Laser-induced breakdown spectroscopy: Extending its application to soil pH measurements
Acid–base equilibria are involved in almost all the processes that occur in soil. The bioavailability of nutrients for plants, for instance, depends on the solubilization of mineral nutrients in the soil solution, which is a pH-dependent process. The determination of pH in soil solutions is usually...
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Published in | Spectrochimica acta. Part B: Atomic spectroscopy Vol. 110; pp. 96 - 99 |
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Format | Journal Article |
Language | English |
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01.08.2015
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Abstract | Acid–base equilibria are involved in almost all the processes that occur in soil. The bioavailability of nutrients for plants, for instance, depends on the solubilization of mineral nutrients in the soil solution, which is a pH-dependent process. The determination of pH in soil solutions is usually carried out by potentiometry using a glass membrane electrode, after extracting some of the soil components with water or CaCl2 solution. The present work describes a simple method for determining the pH of soil, using laser-induced breakdown spectroscopy (LIBS). Sixty samples presenting different textural composition and pH (previously determined by potentiometry) were employed. The samples were divided into a calibration set with fifty samples and a validation set with ten samples. LIBS spectra were recorded for each pelleted sample using laser pulse energy of 115mJ. The intensities of thirty-two emission lines for Al, Ca, H, and O were used to fit a partial least squares (PLS) model. The model was validated by prediction of the pH of the validation set samples, which showed good agreement with the reference values. The prediction mean absolute error was 0.3 pH units and the root mean square error of the prediction was 0.4. These results highlight the potential of LIBS for use in other applications beyond elemental composition determinations. For soil analysis, the proposed method offers the possibility of determining pH, in addition to nutrients and contaminants, using a single LIBS measurement.
•Physical, chemical, and biological properties of soil are influenced by pH.•The pH of mineral soils is normally determined in slurries of water and soil sample by potentiometric measurements.•The association of LIBS elemental emissions with multivariate strategies of analysis has become LIBS a powerful technique.•LIBS was unprecedentedly applied for direct pH determination in different kinds of soil sample.•The clean and fast proposed method encloses the possibility of pH determination in addition of nutrients and contaminants using a single LIBS measurement. |
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AbstractList | Acid–base equilibria are involved in almost all the processes that occur in soil. The bioavailability of nutrients for plants, for instance, depends on the solubilization of mineral nutrients in the soil solution, which is a pH-dependent process. The determination of pH in soil solutions is usually carried out by potentiometry using a glass membrane electrode, after extracting some of the soil components with water or CaCl2 solution. The present work describes a simple method for determining the pH of soil, using laser-induced breakdown spectroscopy (LIBS). Sixty samples presenting different textural composition and pH (previously determined by potentiometry) were employed. The samples were divided into a calibration set with fifty samples and a validation set with ten samples. LIBS spectra were recorded for each pelleted sample using laser pulse energy of 115mJ. The intensities of thirty-two emission lines for Al, Ca, H, and O were used to fit a partial least squares (PLS) model. The model was validated by prediction of the pH of the validation set samples, which showed good agreement with the reference values. The prediction mean absolute error was 0.3 pH units and the root mean square error of the prediction was 0.4. These results highlight the potential of LIBS for use in other applications beyond elemental composition determinations. For soil analysis, the proposed method offers the possibility of determining pH, in addition to nutrients and contaminants, using a single LIBS measurement.
•Physical, chemical, and biological properties of soil are influenced by pH.•The pH of mineral soils is normally determined in slurries of water and soil sample by potentiometric measurements.•The association of LIBS elemental emissions with multivariate strategies of analysis has become LIBS a powerful technique.•LIBS was unprecedentedly applied for direct pH determination in different kinds of soil sample.•The clean and fast proposed method encloses the possibility of pH determination in addition of nutrients and contaminants using a single LIBS measurement. Acid-base equilibria are involved in almost all the processes that occur in soil. The bioavailability of nutrients for plants, for instance, depends on the solubilization of mineral nutrients in the soil solution, which is a pH-dependent process. The determination of pH in soil solutions is usually carried out by potentiometry using a glass membrane electrode, after extracting some of the soil components with water or CaCl2 solution. The present work describes a simple method for determining the pH of soil, using laser-induced breakdown spectroscopy (LIBS). Sixty samples presenting different textural composition and pH (previously determined by potentiometry) were employed. The samples were divided into a calibration set with fifty samples and a validation set with ten samples. LIBS spectra were recorded for each pelleted sample using laser pulse energy of 115mJ. The intensities of thirty-two emission lines for Al, Ca, H, and O were used to fit a partial least squares (PLS) model. The model was validated by prediction of the pH of the validation set samples, which showed good agreement with the reference values. The prediction mean absolute error was 0.3 pH units and the root mean square error of the prediction was 0.4. These results highlight the potential of LIBS for use in other applications beyond elemental composition determinations. For soil analysis, the proposed method offers the possibility of determining pH, in addition to nutrients and contaminants, using a single LIBS measurement. |
Author | Ferreira, Edilene Cristina Gomes Neto, José A. Ferreira, Ednaldo José Milori, Débora M.B.P. Anzano, Jesús Manuel |
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Cites_doi | 10.1093/jaoac/78.2.310 10.1016/j.sab.2008.09.008 10.1145/1656274.1656278 10.2136/sssaj1955.03615995001900020013x 10.1366/11-06574 10.1097/00010694-196101000-00004 |
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References | Coleman, Craig (bb0055) 1961; 91 Cremers, Radziemski (bb0040) 2006 Kalra (bb0020) 1995; 78 Skoog, West, Holler (bb0025) 1992 Tisdale, Nelson (bb0050) 1966 Miziolek, Palleschi, Schechter (bb0030) 2012 Hall, Frank, Holmes, Pfahringer, Reutemann, Witten (bb0045) 2009; 11 Bousquet, Travaillé, Ismaël, Canioni, Michel-Le Pierrès, Brasseur, Roy, le Hecho, Larregieu, Tellier, Potin-Gautier, Boriachon, Wazen, Diard, Belbèze (bb0060) 2008; 63 Hahn, Omenetto (bb0035) 2012; 66 McLean (bb0005) 1982 Schofield, Taylor (bb0015) 1955; 19 Jones (bb0010) 2012 Skoog (10.1016/j.sab.2015.06.002_bb0025) 1992 Cremers (10.1016/j.sab.2015.06.002_bb0040) 2006 Schofield (10.1016/j.sab.2015.06.002_bb0015) 1955; 19 Bousquet (10.1016/j.sab.2015.06.002_bb0060) 2008; 63 McLean (10.1016/j.sab.2015.06.002_bb0005) 1982 Miziolek (10.1016/j.sab.2015.06.002_bb0030) 2012 Jones (10.1016/j.sab.2015.06.002_bb0010) 2012 Coleman (10.1016/j.sab.2015.06.002_bb0055) 1961; 91 Kalra (10.1016/j.sab.2015.06.002_bb0020) 1995; 78 Hall (10.1016/j.sab.2015.06.002_bb0045) 2009; 11 Tisdale (10.1016/j.sab.2015.06.002_bb0050) 1966 Hahn (10.1016/j.sab.2015.06.002_bb0035) 2012; 66 |
References_xml | – volume: 19 start-page: 164 year: 1955 end-page: 167 ident: bb0015 article-title: The measurement of soil pH publication-title: Soil Sci. Soc. Am. Proc. contributor: fullname: Taylor – volume: 91 start-page: 14 year: 1961 end-page: 18 ident: bb0055 article-title: The spontaneous alteration of hydrogen clay publication-title: Soil Sci. contributor: fullname: Craig – volume: 78 start-page: 310 year: 1995 end-page: 324 ident: bb0020 article-title: Determination of pH of soils by different methods: collaborative study publication-title: J. AOAC Int. contributor: fullname: Kalra – year: 1992 ident: bb0025 article-title: Fundamentals of Analytical Chemistry contributor: fullname: Holler – volume: 66 start-page: 347 year: 2012 end-page: 419 ident: bb0035 article-title: Laser-induced breakdown spectroscopy (LIBS). Part II: Review of instrumental and methodological approaches to material analysis and applications to different fields publication-title: Appl. Spectrosc. contributor: fullname: Omenetto – year: 2012 ident: bb0030 article-title: Laser Induced Breakdown Spectroscopy—Fundamentals and Applications contributor: fullname: Schechter – year: 1966 ident: bb0050 article-title: Soil Fertility and Fertilizers contributor: fullname: Nelson – volume: 63 start-page: 1085 year: 2008 end-page: 1090 ident: bb0060 article-title: Development of a mobile system based on laser-induced breakdown spectroscopy and dedicated to in situ analysis of polluted soils publication-title: Spectrochim. Acta Part B contributor: fullname: Belbèze – start-page: 199 year: 1982 end-page: 224 ident: bb0005 article-title: Soil pH and Lime Requirement publication-title: Methods of Soil Analysis. Part 2. Chemical and Microbiological Properties contributor: fullname: McLean – year: 2006 ident: bb0040 article-title: Handbook of Laser-Induced Breakdown Spectroscopy contributor: fullname: Radziemski – volume: 11 start-page: 10 year: 2009 end-page: 17 ident: bb0045 article-title: The WEKA data mining software: an update publication-title: SIGKDD Explor. contributor: fullname: Witten – year: 2012 ident: bb0010 article-title: Plant Nutrition and Soil Fertility Manual contributor: fullname: Jones – year: 1992 ident: 10.1016/j.sab.2015.06.002_bb0025 contributor: fullname: Skoog – year: 2012 ident: 10.1016/j.sab.2015.06.002_bb0030 contributor: fullname: Miziolek – start-page: 199 year: 1982 ident: 10.1016/j.sab.2015.06.002_bb0005 article-title: Soil pH and Lime Requirement contributor: fullname: McLean – volume: 78 start-page: 310 year: 1995 ident: 10.1016/j.sab.2015.06.002_bb0020 article-title: Determination of pH of soils by different methods: collaborative study publication-title: J. AOAC Int. doi: 10.1093/jaoac/78.2.310 contributor: fullname: Kalra – year: 1966 ident: 10.1016/j.sab.2015.06.002_bb0050 contributor: fullname: Tisdale – volume: 63 start-page: 1085 year: 2008 ident: 10.1016/j.sab.2015.06.002_bb0060 article-title: Development of a mobile system based on laser-induced breakdown spectroscopy and dedicated to in situ analysis of polluted soils publication-title: Spectrochim. Acta Part B doi: 10.1016/j.sab.2008.09.008 contributor: fullname: Bousquet – year: 2006 ident: 10.1016/j.sab.2015.06.002_bb0040 contributor: fullname: Cremers – volume: 11 start-page: 10 year: 2009 ident: 10.1016/j.sab.2015.06.002_bb0045 article-title: The WEKA data mining software: an update publication-title: SIGKDD Explor. doi: 10.1145/1656274.1656278 contributor: fullname: Hall – year: 2012 ident: 10.1016/j.sab.2015.06.002_bb0010 contributor: fullname: Jones – volume: 19 start-page: 164 year: 1955 ident: 10.1016/j.sab.2015.06.002_bb0015 article-title: The measurement of soil pH publication-title: Soil Sci. Soc. Am. Proc. doi: 10.2136/sssaj1955.03615995001900020013x contributor: fullname: Schofield – volume: 66 start-page: 347 year: 2012 ident: 10.1016/j.sab.2015.06.002_bb0035 article-title: Laser-induced breakdown spectroscopy (LIBS). Part II: Review of instrumental and methodological approaches to material analysis and applications to different fields publication-title: Appl. Spectrosc. doi: 10.1366/11-06574 contributor: fullname: Hahn – volume: 91 start-page: 14 year: 1961 ident: 10.1016/j.sab.2015.06.002_bb0055 article-title: The spontaneous alteration of hydrogen clay publication-title: Soil Sci. doi: 10.1097/00010694-196101000-00004 contributor: fullname: Coleman |
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Snippet | Acid–base equilibria are involved in almost all the processes that occur in soil. The bioavailability of nutrients for plants, for instance, depends on the... Acid-base equilibria are involved in almost all the processes that occur in soil. The bioavailability of nutrients for plants, for instance, depends on the... |
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