Abstract

Laser-induced breakdown spectroscopy (LIBS) is an analytical technique real-time geochemical analysis that is being developed for portable use outside of the laboratory. In this study, statistical signal processing and classification techniques were applied to single-shot, broadband LIBS spectra, comprising measured plasma light intensities between 200 and 960 nm, for a suite of 157 garnets of different composition from 92 locations worldwide. Partial least squares discriminant analysis was applied to sets of 25 LIBS spectra for each garnet sample and used to classify the garnet samples based on composition and geographic origin. Careful consideration was given to the cross-validation procedure to ensure that the classification algorithm is robust to unseen data. The results indicate that broadband LIBS analysis can be used to discriminate garnets of different composition and has the potential to discern geographic origin.

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  1. R. S. Harmon, F. C. DeLucia Jr., A. W. Miziolek, K. L. McNesby, R. A. Walters, and P. D. French, “Laser-induced breakdown spectroscopy (LIBS)--an emerging field-portable sensor technology for real-time, in situ geochemical and environmental analysis,” Geochem. Explor. Environ. Anal. 5, 21-28 (2005).
  2. R. S. Harmon, F. C. DeLucia Jr., C. E. McManus, N. J. McMillan, T. F. Jenkins, M. E. Walsh, and A. W. Miziolek, “Laser-induced breakdown spectroscopy--an emerging chemical sensor technology for field-portable, real-time geochemical, mineralogical, and environmental applications,” Appl. Geochem. 21, 730-747 (2005).
  3. R. S. Harmon, J. Remus, N. J. McMillan, C. McManus, L. Collins, and J. L. Gottfried, “LIBS analysis of geomaterials: geochemical fingerprinting for the rapid analysis and discrimination of minerals,” Appl. Geochem . 24, 1125-1141 (2008).
  4. N. J. McMillan, C. E. McManus, R. S. Harmon, F. C. DeLucia Jr., and A. W. Miziolek, “Laser-induced breakdown spectroscopy analysis of complex silicate minerals--Beryl,” Anal. Bioanal. Chem. 385, 263-271 (2006).
    [CrossRef]
  5. N. J. McMillan, R. S. Harmon, F. C. De Lucia Jr., and A. W. Miziolek, “Laser-induced breakdown spectroscopy analysis of minerals--carbonates and silicates,” Spectrochim. Acta Part B 62, 1578-1536 (2007).
  6. C. E. McManus, N. J. McMillan, R. S. Harmon, R. C. Whitmore, F. C. DeLucia Jr., and A. W. Miziolek, “The use of laser induced breakdown spectroscopy (LIBS) in the determination of gem provenance--Beryls,” Appl. Opt. 47, G72-G79 (2008).
    [CrossRef]
  7. J. L. Gottfried, R. S. Harmon, F. C. De Lucia Jr., and A. W. Miziolek, “Multivariate analysis of LIBS spectra for geomaterial classification,” Spectrochim. Acta Part B 64, 1009-1019(2009).
    [CrossRef]
  8. W. A. Deer, R. A. Howie, and J. Zussman, Rock-Forming Minerals, Volume 1. Ortho- and Ring Silicates (Longman Press, 1975).
  9. W. E. Ford, “A study of the relations existing between the chemical, optical, and other physical properties of the members of the garnet group,” Am. J. Sci. 40, 33-49 (1919).
  10. M. J. Fleisher, “The relation between chemical composition and physical properties in the garnet group,” Am. Mineral. 22, 751-758 (1937).
  11. C. S. Hurlbut and C. Klein, Manual of Mineralogy (Wiley, 1977).
  12. J. W. Anthony, R. A. Bideaux, K. W. Bladh, and M. C. Nichols, Handbook of Mineralogy (Mineralogical Society of America, 2001); http://www.handbookofmineralogy.org/pdfs/Pyrope.PDF, http://www.handbookofmineralogy.org/Almandine.PDF, http://www.handbookofmineralogy.org/Andradite.PDF, http://www.handbookofmineralogy.org/Grossular.PDF, http://www.handbookofmineralogy.org/Spessartine.PDF, http://www.handbookofmineralogy.org/Uvarovite.PDF.
  13. J. Ganguly and J. C. Kennedy, “The energetics of natural garnet solid solution,” Contrib. Mineral. Petrol. 48, 137-148(1974).
    [CrossRef]
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  15. J. Ito and C. Frondel, “Synthesis of the grossularite-spessartite series,” Am. Mineral. 53, 1036-1038 (1968).
  16. J. Ito and C. Frondel, “Stilpnomelane and spessartite-grossularite from Franklin, New Jersey,” Am. Mineral. 50, 498-501 (1965).
  17. R. J. Tracy, P. Robinson, and A. B. Thompson, “Garnet composition and zoning in the determination of temperature and pressure of metamorphism, central Massachusetts,” Am. Mineral. 61, 762-775 (1976).
  18. T. P. Loomis, “Reaction of zoning of garnet,” Contrib. Mineral. Petrol. 52, 285-305 (1975).
    [CrossRef]
  19. W. H. Blackburn, “Zoned and unzoned garnets from the Grenville gneisses around Gananoque, Ontario,” Canad. Mineral 9, 691-698 (1969).
  20. D. Smith and F. R. Boyd, “Compositional zonation in garnets in peridotite xenoliths,” Contrib. Mineral Petrol. 112, 134-147 (1992).
    [CrossRef]
  21. B. M. Loeffler and R. G. Burns, “Shedding light on the color of gems and minerals,” Am. Scientist 64, 636-647 (1976).
  22. K. Nassau, “The origin of color in minerals,” Am. Mineral. 63, 219-229 (1978).
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  25. S. Wold, M. Sjöström, and L. Eriksson, “PLS-regression: a basic tool of chemometrics,” Chemometr. Intel. Lab. Syst. 58, 109-130 (2001).
  26. C. M. Bishop, Pattern Recognition and Machine Learning (Springer, 2007).
  27. J. E. Gentle, Matrix Algebra: Theory, Computations, and Applications in Statistics (Springer, 2007).
  28. I.-G. Chong and C.-H. Jun, “Performance of some variable selection methods when multicollinearity is present,” Chemometr. Intel. Lab. Syst. 78, 103-112 (2005).

2009

J. L. Gottfried, R. S. Harmon, F. C. De Lucia Jr., and A. W. Miziolek, “Multivariate analysis of LIBS spectra for geomaterial classification,” Spectrochim. Acta Part B 64, 1009-1019(2009).
[CrossRef]

2008

R. S. Harmon, J. Remus, N. J. McMillan, C. McManus, L. Collins, and J. L. Gottfried, “LIBS analysis of geomaterials: geochemical fingerprinting for the rapid analysis and discrimination of minerals,” Appl. Geochem . 24, 1125-1141 (2008).

C. E. McManus, N. J. McMillan, R. S. Harmon, R. C. Whitmore, F. C. DeLucia Jr., and A. W. Miziolek, “The use of laser induced breakdown spectroscopy (LIBS) in the determination of gem provenance--Beryls,” Appl. Opt. 47, G72-G79 (2008).
[CrossRef]

2007

N. J. McMillan, R. S. Harmon, F. C. De Lucia Jr., and A. W. Miziolek, “Laser-induced breakdown spectroscopy analysis of minerals--carbonates and silicates,” Spectrochim. Acta Part B 62, 1578-1536 (2007).

2006

N. J. McMillan, C. E. McManus, R. S. Harmon, F. C. DeLucia Jr., and A. W. Miziolek, “Laser-induced breakdown spectroscopy analysis of complex silicate minerals--Beryl,” Anal. Bioanal. Chem. 385, 263-271 (2006).
[CrossRef]

2005

I.-G. Chong and C.-H. Jun, “Performance of some variable selection methods when multicollinearity is present,” Chemometr. Intel. Lab. Syst. 78, 103-112 (2005).

R. S. Harmon, F. C. DeLucia Jr., A. W. Miziolek, K. L. McNesby, R. A. Walters, and P. D. French, “Laser-induced breakdown spectroscopy (LIBS)--an emerging field-portable sensor technology for real-time, in situ geochemical and environmental analysis,” Geochem. Explor. Environ. Anal. 5, 21-28 (2005).

R. S. Harmon, F. C. DeLucia Jr., C. E. McManus, N. J. McMillan, T. F. Jenkins, M. E. Walsh, and A. W. Miziolek, “Laser-induced breakdown spectroscopy--an emerging chemical sensor technology for field-portable, real-time geochemical, mineralogical, and environmental applications,” Appl. Geochem. 21, 730-747 (2005).

2001

S. Wold, M. Sjöström, and L. Eriksson, “PLS-regression: a basic tool of chemometrics,” Chemometr. Intel. Lab. Syst. 58, 109-130 (2001).

1992

D. Smith and F. R. Boyd, “Compositional zonation in garnets in peridotite xenoliths,” Contrib. Mineral Petrol. 112, 134-147 (1992).
[CrossRef]

1978

K. Nassau, “The origin of color in minerals,” Am. Mineral. 63, 219-229 (1978).

1976

B. M. Loeffler and R. G. Burns, “Shedding light on the color of gems and minerals,” Am. Scientist 64, 636-647 (1976).

R. J. Tracy, P. Robinson, and A. B. Thompson, “Garnet composition and zoning in the determination of temperature and pressure of metamorphism, central Massachusetts,” Am. Mineral. 61, 762-775 (1976).

R. J. Tracy, P. Robinson, and A. B. Thompson, “Garnet composition and zoning in the determination of temperature and pressure of metamorphism, central Massachusetts,” Am. Mineral. 61, 762-775 (1976).

1975

T. P. Loomis, “Reaction of zoning of garnet,” Contrib. Mineral. Petrol. 52, 285-305 (1975).
[CrossRef]

1974

J. Ganguly and J. C. Kennedy, “The energetics of natural garnet solid solution,” Contrib. Mineral. Petrol. 48, 137-148(1974).
[CrossRef]

1969

W. H. Blackburn, “Zoned and unzoned garnets from the Grenville gneisses around Gananoque, Ontario,” Canad. Mineral 9, 691-698 (1969).

1968

J. Ito and C. Frondel, “Synthesis of the grossularite-spessartite series,” Am. Mineral. 53, 1036-1038 (1968).

1965

J. Ito and C. Frondel, “Stilpnomelane and spessartite-grossularite from Franklin, New Jersey,” Am. Mineral. 50, 498-501 (1965).

1937

M. J. Fleisher, “The relation between chemical composition and physical properties in the garnet group,” Am. Mineral. 22, 751-758 (1937).

1919

W. E. Ford, “A study of the relations existing between the chemical, optical, and other physical properties of the members of the garnet group,” Am. J. Sci. 40, 33-49 (1919).

Anthony, J. W.

J. W. Anthony, R. A. Bideaux, K. W. Bladh, and M. C. Nichols, Handbook of Mineralogy (Mineralogical Society of America, 2001); http://www.handbookofmineralogy.org/pdfs/Pyrope.PDF, http://www.handbookofmineralogy.org/Almandine.PDF, http://www.handbookofmineralogy.org/Andradite.PDF, http://www.handbookofmineralogy.org/Grossular.PDF, http://www.handbookofmineralogy.org/Spessartine.PDF, http://www.handbookofmineralogy.org/Uvarovite.PDF.

Bideaux, R. A.

J. W. Anthony, R. A. Bideaux, K. W. Bladh, and M. C. Nichols, Handbook of Mineralogy (Mineralogical Society of America, 2001); http://www.handbookofmineralogy.org/pdfs/Pyrope.PDF, http://www.handbookofmineralogy.org/Almandine.PDF, http://www.handbookofmineralogy.org/Andradite.PDF, http://www.handbookofmineralogy.org/Grossular.PDF, http://www.handbookofmineralogy.org/Spessartine.PDF, http://www.handbookofmineralogy.org/Uvarovite.PDF.

Bishop, C. M.

C. M. Bishop, Pattern Recognition and Machine Learning (Springer, 2007).

Blackburn, W. H.

W. H. Blackburn, “Zoned and unzoned garnets from the Grenville gneisses around Gananoque, Ontario,” Canad. Mineral 9, 691-698 (1969).

Bladh, K. W.

J. W. Anthony, R. A. Bideaux, K. W. Bladh, and M. C. Nichols, Handbook of Mineralogy (Mineralogical Society of America, 2001); http://www.handbookofmineralogy.org/pdfs/Pyrope.PDF, http://www.handbookofmineralogy.org/Almandine.PDF, http://www.handbookofmineralogy.org/Andradite.PDF, http://www.handbookofmineralogy.org/Grossular.PDF, http://www.handbookofmineralogy.org/Spessartine.PDF, http://www.handbookofmineralogy.org/Uvarovite.PDF.

Boyd, F. R.

D. Smith and F. R. Boyd, “Compositional zonation in garnets in peridotite xenoliths,” Contrib. Mineral Petrol. 112, 134-147 (1992).
[CrossRef]

Burns, R. G.

B. M. Loeffler and R. G. Burns, “Shedding light on the color of gems and minerals,” Am. Scientist 64, 636-647 (1976).

Chong, I.-G.

I.-G. Chong and C.-H. Jun, “Performance of some variable selection methods when multicollinearity is present,” Chemometr. Intel. Lab. Syst. 78, 103-112 (2005).

Collins, L.

R. S. Harmon, J. Remus, N. J. McMillan, C. McManus, L. Collins, and J. L. Gottfried, “LIBS analysis of geomaterials: geochemical fingerprinting for the rapid analysis and discrimination of minerals,” Appl. Geochem . 24, 1125-1141 (2008).

De Lucia, F. C.

J. L. Gottfried, R. S. Harmon, F. C. De Lucia Jr., and A. W. Miziolek, “Multivariate analysis of LIBS spectra for geomaterial classification,” Spectrochim. Acta Part B 64, 1009-1019(2009).
[CrossRef]

N. J. McMillan, R. S. Harmon, F. C. De Lucia Jr., and A. W. Miziolek, “Laser-induced breakdown spectroscopy analysis of minerals--carbonates and silicates,” Spectrochim. Acta Part B 62, 1578-1536 (2007).

Deer, W. A.

W. A. Deer, R. A. Howie, and J. Zussman, Rock-Forming Minerals, Volume 1. Ortho- and Ring Silicates (Longman Press, 1975).

DeLucia, F. C.

C. E. McManus, N. J. McMillan, R. S. Harmon, R. C. Whitmore, F. C. DeLucia Jr., and A. W. Miziolek, “The use of laser induced breakdown spectroscopy (LIBS) in the determination of gem provenance--Beryls,” Appl. Opt. 47, G72-G79 (2008).
[CrossRef]

N. J. McMillan, C. E. McManus, R. S. Harmon, F. C. DeLucia Jr., and A. W. Miziolek, “Laser-induced breakdown spectroscopy analysis of complex silicate minerals--Beryl,” Anal. Bioanal. Chem. 385, 263-271 (2006).
[CrossRef]

R. S. Harmon, F. C. DeLucia Jr., A. W. Miziolek, K. L. McNesby, R. A. Walters, and P. D. French, “Laser-induced breakdown spectroscopy (LIBS)--an emerging field-portable sensor technology for real-time, in situ geochemical and environmental analysis,” Geochem. Explor. Environ. Anal. 5, 21-28 (2005).

R. S. Harmon, F. C. DeLucia Jr., C. E. McManus, N. J. McMillan, T. F. Jenkins, M. E. Walsh, and A. W. Miziolek, “Laser-induced breakdown spectroscopy--an emerging chemical sensor technology for field-portable, real-time geochemical, mineralogical, and environmental applications,” Appl. Geochem. 21, 730-747 (2005).

Eriksson, L.

S. Wold, M. Sjöström, and L. Eriksson, “PLS-regression: a basic tool of chemometrics,” Chemometr. Intel. Lab. Syst. 58, 109-130 (2001).

Fleisher, M. J.

M. J. Fleisher, “The relation between chemical composition and physical properties in the garnet group,” Am. Mineral. 22, 751-758 (1937).

Ford, W. E.

W. E. Ford, “A study of the relations existing between the chemical, optical, and other physical properties of the members of the garnet group,” Am. J. Sci. 40, 33-49 (1919).

French, P. D.

R. S. Harmon, F. C. DeLucia Jr., A. W. Miziolek, K. L. McNesby, R. A. Walters, and P. D. French, “Laser-induced breakdown spectroscopy (LIBS)--an emerging field-portable sensor technology for real-time, in situ geochemical and environmental analysis,” Geochem. Explor. Environ. Anal. 5, 21-28 (2005).

Frondel, C.

J. Ito and C. Frondel, “Synthesis of the grossularite-spessartite series,” Am. Mineral. 53, 1036-1038 (1968).

J. Ito and C. Frondel, “Stilpnomelane and spessartite-grossularite from Franklin, New Jersey,” Am. Mineral. 50, 498-501 (1965).

Ganguly, J.

J. Ganguly and J. C. Kennedy, “The energetics of natural garnet solid solution,” Contrib. Mineral. Petrol. 48, 137-148(1974).
[CrossRef]

Gentle, J. E.

J. E. Gentle, Matrix Algebra: Theory, Computations, and Applications in Statistics (Springer, 2007).

Gottfried, J. L.

J. L. Gottfried, R. S. Harmon, F. C. De Lucia Jr., and A. W. Miziolek, “Multivariate analysis of LIBS spectra for geomaterial classification,” Spectrochim. Acta Part B 64, 1009-1019(2009).
[CrossRef]

R. S. Harmon, J. Remus, N. J. McMillan, C. McManus, L. Collins, and J. L. Gottfried, “LIBS analysis of geomaterials: geochemical fingerprinting for the rapid analysis and discrimination of minerals,” Appl. Geochem . 24, 1125-1141 (2008).

Harmon, R. S.

J. L. Gottfried, R. S. Harmon, F. C. De Lucia Jr., and A. W. Miziolek, “Multivariate analysis of LIBS spectra for geomaterial classification,” Spectrochim. Acta Part B 64, 1009-1019(2009).
[CrossRef]

R. S. Harmon, J. Remus, N. J. McMillan, C. McManus, L. Collins, and J. L. Gottfried, “LIBS analysis of geomaterials: geochemical fingerprinting for the rapid analysis and discrimination of minerals,” Appl. Geochem . 24, 1125-1141 (2008).

C. E. McManus, N. J. McMillan, R. S. Harmon, R. C. Whitmore, F. C. DeLucia Jr., and A. W. Miziolek, “The use of laser induced breakdown spectroscopy (LIBS) in the determination of gem provenance--Beryls,” Appl. Opt. 47, G72-G79 (2008).
[CrossRef]

N. J. McMillan, R. S. Harmon, F. C. De Lucia Jr., and A. W. Miziolek, “Laser-induced breakdown spectroscopy analysis of minerals--carbonates and silicates,” Spectrochim. Acta Part B 62, 1578-1536 (2007).

N. J. McMillan, C. E. McManus, R. S. Harmon, F. C. DeLucia Jr., and A. W. Miziolek, “Laser-induced breakdown spectroscopy analysis of complex silicate minerals--Beryl,” Anal. Bioanal. Chem. 385, 263-271 (2006).
[CrossRef]

R. S. Harmon, F. C. DeLucia Jr., A. W. Miziolek, K. L. McNesby, R. A. Walters, and P. D. French, “Laser-induced breakdown spectroscopy (LIBS)--an emerging field-portable sensor technology for real-time, in situ geochemical and environmental analysis,” Geochem. Explor. Environ. Anal. 5, 21-28 (2005).

R. S. Harmon, F. C. DeLucia Jr., C. E. McManus, N. J. McMillan, T. F. Jenkins, M. E. Walsh, and A. W. Miziolek, “Laser-induced breakdown spectroscopy--an emerging chemical sensor technology for field-portable, real-time geochemical, mineralogical, and environmental applications,” Appl. Geochem. 21, 730-747 (2005).

Howie, R. A.

W. A. Deer, R. A. Howie, and J. Zussman, Rock-Forming Minerals, Volume 1. Ortho- and Ring Silicates (Longman Press, 1975).

Hurlbut, C. S.

C. S. Hurlbut and C. Klein, Manual of Mineralogy (Wiley, 1977).

Ito, J.

J. Ito and C. Frondel, “Synthesis of the grossularite-spessartite series,” Am. Mineral. 53, 1036-1038 (1968).

J. Ito and C. Frondel, “Stilpnomelane and spessartite-grossularite from Franklin, New Jersey,” Am. Mineral. 50, 498-501 (1965).

Jenkins, T. F.

R. S. Harmon, F. C. DeLucia Jr., C. E. McManus, N. J. McMillan, T. F. Jenkins, M. E. Walsh, and A. W. Miziolek, “Laser-induced breakdown spectroscopy--an emerging chemical sensor technology for field-portable, real-time geochemical, mineralogical, and environmental applications,” Appl. Geochem. 21, 730-747 (2005).

Jun, C.-H.

I.-G. Chong and C.-H. Jun, “Performance of some variable selection methods when multicollinearity is present,” Chemometr. Intel. Lab. Syst. 78, 103-112 (2005).

Kennedy, J. C.

J. Ganguly and J. C. Kennedy, “The energetics of natural garnet solid solution,” Contrib. Mineral. Petrol. 48, 137-148(1974).
[CrossRef]

Klein, C.

C. S. Hurlbut and C. Klein, Manual of Mineralogy (Wiley, 1977).

Kramida, A. E.

Y. Ralchenko, A. E. Kramida, J. Reader, and NIST ASD Team, NIST Atomic Spectra Database (version 3.1.5) (National Institute of Standards and Technology, 2008); available online, http://physics.nist.gov/asd3.

Loeffler, B. M.

B. M. Loeffler and R. G. Burns, “Shedding light on the color of gems and minerals,” Am. Scientist 64, 636-647 (1976).

Loomis, T. P.

T. P. Loomis, “Reaction of zoning of garnet,” Contrib. Mineral. Petrol. 52, 285-305 (1975).
[CrossRef]

McManus, C.

R. S. Harmon, J. Remus, N. J. McMillan, C. McManus, L. Collins, and J. L. Gottfried, “LIBS analysis of geomaterials: geochemical fingerprinting for the rapid analysis and discrimination of minerals,” Appl. Geochem . 24, 1125-1141 (2008).

McManus, C. E.

C. E. McManus, N. J. McMillan, R. S. Harmon, R. C. Whitmore, F. C. DeLucia Jr., and A. W. Miziolek, “The use of laser induced breakdown spectroscopy (LIBS) in the determination of gem provenance--Beryls,” Appl. Opt. 47, G72-G79 (2008).
[CrossRef]

N. J. McMillan, C. E. McManus, R. S. Harmon, F. C. DeLucia Jr., and A. W. Miziolek, “Laser-induced breakdown spectroscopy analysis of complex silicate minerals--Beryl,” Anal. Bioanal. Chem. 385, 263-271 (2006).
[CrossRef]

R. S. Harmon, F. C. DeLucia Jr., C. E. McManus, N. J. McMillan, T. F. Jenkins, M. E. Walsh, and A. W. Miziolek, “Laser-induced breakdown spectroscopy--an emerging chemical sensor technology for field-portable, real-time geochemical, mineralogical, and environmental applications,” Appl. Geochem. 21, 730-747 (2005).

McMillan, N. J.

R. S. Harmon, J. Remus, N. J. McMillan, C. McManus, L. Collins, and J. L. Gottfried, “LIBS analysis of geomaterials: geochemical fingerprinting for the rapid analysis and discrimination of minerals,” Appl. Geochem . 24, 1125-1141 (2008).

C. E. McManus, N. J. McMillan, R. S. Harmon, R. C. Whitmore, F. C. DeLucia Jr., and A. W. Miziolek, “The use of laser induced breakdown spectroscopy (LIBS) in the determination of gem provenance--Beryls,” Appl. Opt. 47, G72-G79 (2008).
[CrossRef]

N. J. McMillan, R. S. Harmon, F. C. De Lucia Jr., and A. W. Miziolek, “Laser-induced breakdown spectroscopy analysis of minerals--carbonates and silicates,” Spectrochim. Acta Part B 62, 1578-1536 (2007).

N. J. McMillan, C. E. McManus, R. S. Harmon, F. C. DeLucia Jr., and A. W. Miziolek, “Laser-induced breakdown spectroscopy analysis of complex silicate minerals--Beryl,” Anal. Bioanal. Chem. 385, 263-271 (2006).
[CrossRef]

R. S. Harmon, F. C. DeLucia Jr., C. E. McManus, N. J. McMillan, T. F. Jenkins, M. E. Walsh, and A. W. Miziolek, “Laser-induced breakdown spectroscopy--an emerging chemical sensor technology for field-portable, real-time geochemical, mineralogical, and environmental applications,” Appl. Geochem. 21, 730-747 (2005).

McNesby, K. L.

R. S. Harmon, F. C. DeLucia Jr., A. W. Miziolek, K. L. McNesby, R. A. Walters, and P. D. French, “Laser-induced breakdown spectroscopy (LIBS)--an emerging field-portable sensor technology for real-time, in situ geochemical and environmental analysis,” Geochem. Explor. Environ. Anal. 5, 21-28 (2005).

Miziolek, A. W.

J. L. Gottfried, R. S. Harmon, F. C. De Lucia Jr., and A. W. Miziolek, “Multivariate analysis of LIBS spectra for geomaterial classification,” Spectrochim. Acta Part B 64, 1009-1019(2009).
[CrossRef]

C. E. McManus, N. J. McMillan, R. S. Harmon, R. C. Whitmore, F. C. DeLucia Jr., and A. W. Miziolek, “The use of laser induced breakdown spectroscopy (LIBS) in the determination of gem provenance--Beryls,” Appl. Opt. 47, G72-G79 (2008).
[CrossRef]

N. J. McMillan, R. S. Harmon, F. C. De Lucia Jr., and A. W. Miziolek, “Laser-induced breakdown spectroscopy analysis of minerals--carbonates and silicates,” Spectrochim. Acta Part B 62, 1578-1536 (2007).

N. J. McMillan, C. E. McManus, R. S. Harmon, F. C. DeLucia Jr., and A. W. Miziolek, “Laser-induced breakdown spectroscopy analysis of complex silicate minerals--Beryl,” Anal. Bioanal. Chem. 385, 263-271 (2006).
[CrossRef]

R. S. Harmon, F. C. DeLucia Jr., A. W. Miziolek, K. L. McNesby, R. A. Walters, and P. D. French, “Laser-induced breakdown spectroscopy (LIBS)--an emerging field-portable sensor technology for real-time, in situ geochemical and environmental analysis,” Geochem. Explor. Environ. Anal. 5, 21-28 (2005).

R. S. Harmon, F. C. DeLucia Jr., C. E. McManus, N. J. McMillan, T. F. Jenkins, M. E. Walsh, and A. W. Miziolek, “Laser-induced breakdown spectroscopy--an emerging chemical sensor technology for field-portable, real-time geochemical, mineralogical, and environmental applications,” Appl. Geochem. 21, 730-747 (2005).

Nassau, K.

K. Nassau, “The origin of color in minerals,” Am. Mineral. 63, 219-229 (1978).

Nichols, M. C.

J. W. Anthony, R. A. Bideaux, K. W. Bladh, and M. C. Nichols, Handbook of Mineralogy (Mineralogical Society of America, 2001); http://www.handbookofmineralogy.org/pdfs/Pyrope.PDF, http://www.handbookofmineralogy.org/Almandine.PDF, http://www.handbookofmineralogy.org/Andradite.PDF, http://www.handbookofmineralogy.org/Grossular.PDF, http://www.handbookofmineralogy.org/Spessartine.PDF, http://www.handbookofmineralogy.org/Uvarovite.PDF.

Ralchenko, Y.

Y. Ralchenko, A. E. Kramida, J. Reader, and NIST ASD Team, NIST Atomic Spectra Database (version 3.1.5) (National Institute of Standards and Technology, 2008); available online, http://physics.nist.gov/asd3.

Reader, J.

Y. Ralchenko, A. E. Kramida, J. Reader, and NIST ASD Team, NIST Atomic Spectra Database (version 3.1.5) (National Institute of Standards and Technology, 2008); available online, http://physics.nist.gov/asd3.

Remus, J.

R. S. Harmon, J. Remus, N. J. McMillan, C. McManus, L. Collins, and J. L. Gottfried, “LIBS analysis of geomaterials: geochemical fingerprinting for the rapid analysis and discrimination of minerals,” Appl. Geochem . 24, 1125-1141 (2008).

Robinson, P.

R. J. Tracy, P. Robinson, and A. B. Thompson, “Garnet composition and zoning in the determination of temperature and pressure of metamorphism, central Massachusetts,” Am. Mineral. 61, 762-775 (1976).

R. J. Tracy, P. Robinson, and A. B. Thompson, “Garnet composition and zoning in the determination of temperature and pressure of metamorphism, central Massachusetts,” Am. Mineral. 61, 762-775 (1976).

Rossman, G. R.

G. R. Rossman, “The California Institute of Technology Mineral Spectroscopy Database” (California Institute of Technology, 2009); http://minerals.gps.caltech.edu/FILES/Visible/garnet/index.htm.

Sjöström, M.

S. Wold, M. Sjöström, and L. Eriksson, “PLS-regression: a basic tool of chemometrics,” Chemometr. Intel. Lab. Syst. 58, 109-130 (2001).

Smith, D.

D. Smith and F. R. Boyd, “Compositional zonation in garnets in peridotite xenoliths,” Contrib. Mineral Petrol. 112, 134-147 (1992).
[CrossRef]

Thompson, A. B.

R. J. Tracy, P. Robinson, and A. B. Thompson, “Garnet composition and zoning in the determination of temperature and pressure of metamorphism, central Massachusetts,” Am. Mineral. 61, 762-775 (1976).

R. J. Tracy, P. Robinson, and A. B. Thompson, “Garnet composition and zoning in the determination of temperature and pressure of metamorphism, central Massachusetts,” Am. Mineral. 61, 762-775 (1976).

Tracy, R. J.

R. J. Tracy, P. Robinson, and A. B. Thompson, “Garnet composition and zoning in the determination of temperature and pressure of metamorphism, central Massachusetts,” Am. Mineral. 61, 762-775 (1976).

R. J. Tracy, P. Robinson, and A. B. Thompson, “Garnet composition and zoning in the determination of temperature and pressure of metamorphism, central Massachusetts,” Am. Mineral. 61, 762-775 (1976).

Walsh, M. E.

R. S. Harmon, F. C. DeLucia Jr., C. E. McManus, N. J. McMillan, T. F. Jenkins, M. E. Walsh, and A. W. Miziolek, “Laser-induced breakdown spectroscopy--an emerging chemical sensor technology for field-portable, real-time geochemical, mineralogical, and environmental applications,” Appl. Geochem. 21, 730-747 (2005).

Walters, R. A.

R. S. Harmon, F. C. DeLucia Jr., A. W. Miziolek, K. L. McNesby, R. A. Walters, and P. D. French, “Laser-induced breakdown spectroscopy (LIBS)--an emerging field-portable sensor technology for real-time, in situ geochemical and environmental analysis,” Geochem. Explor. Environ. Anal. 5, 21-28 (2005).

Whitmore, R. C.

Wold, S.

S. Wold, M. Sjöström, and L. Eriksson, “PLS-regression: a basic tool of chemometrics,” Chemometr. Intel. Lab. Syst. 58, 109-130 (2001).

Zussman, J.

W. A. Deer, R. A. Howie, and J. Zussman, Rock-Forming Minerals, Volume 1. Ortho- and Ring Silicates (Longman Press, 1975).

Am. J. Sci.

W. E. Ford, “A study of the relations existing between the chemical, optical, and other physical properties of the members of the garnet group,” Am. J. Sci. 40, 33-49 (1919).

Am. Mineral.

M. J. Fleisher, “The relation between chemical composition and physical properties in the garnet group,” Am. Mineral. 22, 751-758 (1937).

R. J. Tracy, P. Robinson, and A. B. Thompson, “Garnet composition and zoning in the determination of temperature and pressure of metamorphism, central Massachusetts,” Am. Mineral. 61, 762-775 (1976).

J. Ito and C. Frondel, “Synthesis of the grossularite-spessartite series,” Am. Mineral. 53, 1036-1038 (1968).

J. Ito and C. Frondel, “Stilpnomelane and spessartite-grossularite from Franklin, New Jersey,” Am. Mineral. 50, 498-501 (1965).

R. J. Tracy, P. Robinson, and A. B. Thompson, “Garnet composition and zoning in the determination of temperature and pressure of metamorphism, central Massachusetts,” Am. Mineral. 61, 762-775 (1976).

K. Nassau, “The origin of color in minerals,” Am. Mineral. 63, 219-229 (1978).

Am. Scientist

B. M. Loeffler and R. G. Burns, “Shedding light on the color of gems and minerals,” Am. Scientist 64, 636-647 (1976).

Anal. Bioanal. Chem.

N. J. McMillan, C. E. McManus, R. S. Harmon, F. C. DeLucia Jr., and A. W. Miziolek, “Laser-induced breakdown spectroscopy analysis of complex silicate minerals--Beryl,” Anal. Bioanal. Chem. 385, 263-271 (2006).
[CrossRef]

Appl. Geochem

R. S. Harmon, J. Remus, N. J. McMillan, C. McManus, L. Collins, and J. L. Gottfried, “LIBS analysis of geomaterials: geochemical fingerprinting for the rapid analysis and discrimination of minerals,” Appl. Geochem . 24, 1125-1141 (2008).

Appl. Geochem.

R. S. Harmon, F. C. DeLucia Jr., C. E. McManus, N. J. McMillan, T. F. Jenkins, M. E. Walsh, and A. W. Miziolek, “Laser-induced breakdown spectroscopy--an emerging chemical sensor technology for field-portable, real-time geochemical, mineralogical, and environmental applications,” Appl. Geochem. 21, 730-747 (2005).

Appl. Opt.

Canad. Mineral

W. H. Blackburn, “Zoned and unzoned garnets from the Grenville gneisses around Gananoque, Ontario,” Canad. Mineral 9, 691-698 (1969).

Chemometr. Intel. Lab. Syst.

S. Wold, M. Sjöström, and L. Eriksson, “PLS-regression: a basic tool of chemometrics,” Chemometr. Intel. Lab. Syst. 58, 109-130 (2001).

I.-G. Chong and C.-H. Jun, “Performance of some variable selection methods when multicollinearity is present,” Chemometr. Intel. Lab. Syst. 78, 103-112 (2005).

Contrib. Mineral Petrol.

D. Smith and F. R. Boyd, “Compositional zonation in garnets in peridotite xenoliths,” Contrib. Mineral Petrol. 112, 134-147 (1992).
[CrossRef]

Contrib. Mineral. Petrol.

J. Ganguly and J. C. Kennedy, “The energetics of natural garnet solid solution,” Contrib. Mineral. Petrol. 48, 137-148(1974).
[CrossRef]

T. P. Loomis, “Reaction of zoning of garnet,” Contrib. Mineral. Petrol. 52, 285-305 (1975).
[CrossRef]

Geochem. Explor. Environ. Anal.

R. S. Harmon, F. C. DeLucia Jr., A. W. Miziolek, K. L. McNesby, R. A. Walters, and P. D. French, “Laser-induced breakdown spectroscopy (LIBS)--an emerging field-portable sensor technology for real-time, in situ geochemical and environmental analysis,” Geochem. Explor. Environ. Anal. 5, 21-28 (2005).

Spectrochim. Acta Part B

N. J. McMillan, R. S. Harmon, F. C. De Lucia Jr., and A. W. Miziolek, “Laser-induced breakdown spectroscopy analysis of minerals--carbonates and silicates,” Spectrochim. Acta Part B 62, 1578-1536 (2007).

J. L. Gottfried, R. S. Harmon, F. C. De Lucia Jr., and A. W. Miziolek, “Multivariate analysis of LIBS spectra for geomaterial classification,” Spectrochim. Acta Part B 64, 1009-1019(2009).
[CrossRef]

Other

W. A. Deer, R. A. Howie, and J. Zussman, Rock-Forming Minerals, Volume 1. Ortho- and Ring Silicates (Longman Press, 1975).

G. R. Rossman, “The California Institute of Technology Mineral Spectroscopy Database” (California Institute of Technology, 2009); http://minerals.gps.caltech.edu/FILES/Visible/garnet/index.htm.

Y. Ralchenko, A. E. Kramida, J. Reader, and NIST ASD Team, NIST Atomic Spectra Database (version 3.1.5) (National Institute of Standards and Technology, 2008); available online, http://physics.nist.gov/asd3.

C. S. Hurlbut and C. Klein, Manual of Mineralogy (Wiley, 1977).

J. W. Anthony, R. A. Bideaux, K. W. Bladh, and M. C. Nichols, Handbook of Mineralogy (Mineralogical Society of America, 2001); http://www.handbookofmineralogy.org/pdfs/Pyrope.PDF, http://www.handbookofmineralogy.org/Almandine.PDF, http://www.handbookofmineralogy.org/Andradite.PDF, http://www.handbookofmineralogy.org/Grossular.PDF, http://www.handbookofmineralogy.org/Spessartine.PDF, http://www.handbookofmineralogy.org/Uvarovite.PDF.

C. M. Bishop, Pattern Recognition and Machine Learning (Springer, 2007).

J. E. Gentle, Matrix Algebra: Theory, Computations, and Applications in Statistics (Springer, 2007).

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