Modeling and prediction of sulfuric acid digestion analyses data from PXRF spectrometry in tropical soils

Sulfuric acid digestion analyses (SAD) provide useful information to environmental studies, in terms of the geochemical balance of nutrients, parent material uniformity, nutrient reserves for perennial crops, and mineralogical composition of the soil clay fraction. Yet, these analyses are costly, time consuming, and generate chemical waste. This work aimed at predicting SAD results from portable X-ray fluorescence (pXRF) spectrometry, which is proposed as a “green chemistry” alternative to the current SAD method. Soil samples developed from different parent materials were analyzed for soil texture and SAD, and scanned with pXRF. The SAD results were predicted from pXRF elemental analyses through simple linear regressions, stepwise multiple linear regressions, and random forest algorithm, with and without incorporation of soil texture data. The modeling was developed with 70 % of the data, while the remaining 30 % was used for validation through calculation of R2, adjusted R2, root mean square error, and mean error. Simple linear regression can accurately predict SAD results of Fe2O3 (R2 0.89), TiO2 (R2 0.96), and P2O5 (R2 0.89). Stepwise regressions provided accurate predictions for Al2O3 (R2 0.87) and Ki - molar weathering index (SiO2/Al2O3) (R2 0.74) by incorporating soil texture data, as well as for SiO2 (R2 0.61). Random forest also provided adequate predictions, especially for Fe2O3 (R2 0.95), and improved results of Kr - molar weathering index (SiO2/(Al2O3 + Fe2O3)) (R2 0.66), by incorporation of soil texture data. Our findings showed that the SAD results could be accurately predicted from pXRF data, decreasing costs, time and the production of laboratory waste.

Modeling and prediction of sulfuric acid digestion analyses data from PXRF spectrometry in tropical soils

Sulfuric acid digestion analyses (SAD) provide useful information to environmental studies, in terms of the geochemical balance of nutrients, parent material uniformity, nutrient reserves for perennial crops, and mineralogical composition of the soil clay fraction. Yet, these analyses are costly, time consuming, and generate chemical waste. This work aimed at predicting SAD results from portable X-ray fluorescence (pXRF) spectrometry, which is proposed as a “green chemistry” alternative to the current SAD method. Soil samples developed from different parent materials were analyzed for soil texture and SAD, and scanned with pXRF. The SAD results were predicted from pXRF elemental analyses through simple linear regressions, stepwise multiple linear regressions, and random forest algorithm, with and without incorporation of soil texture data. The modeling was developed with 70 % of the data, while the remaining 30 % was used for validation through calculation of R2, adjusted R2, root mean square error, and mean error. Simple linear regression can accurately predict SAD results of Fe2O3 (R2 0.89), TiO2 (R2 0.96), and P2O5 (R2 0.89). Stepwise regressions provided accurate predictions for Al2O3 (R2 0.87) and Ki - molar weathering index (SiO2/Al2O3) (R2 0.74) by incorporating soil texture data, as well as for SiO2 (R2 0.61). Random forest also provided adequate predictions, especially for Fe2O3 (R2 0.95), and improved results of Kr - molar weathering index (SiO2/(Al2O3 + Fe2O3)) (R2 0.66), by incorporation of soil texture data. Our findings showed that the SAD results could be accurately predicted from pXRF data, decreasing costs, time and the production of laboratory waste.(AU)

Mineralogia da argila e propriedades químicas de solos do Planalto Norte Catarinense / Clay mineralogy and chemical properties of soils in the north plateau of Santa Catarina state

No Planalto Norte Catarinense são escassas as informações sobre a composição mineralógica dos solos e há poucos perfis de solo descritos e caracterizados para a região. O mapa de solos de Santa Catarina indica predominância de Cambissolos, Neossolos Litólicos e Latossolos, com Gleissolos ocupando áreas de várzeas. Esses solos ocorrem em relevo desde plano até forte ondulado, onde pequenos e médios proprietários rurais desenvolvem cultivos diversificados, com áreas expressivas de reflorestamentos com pinus. Este trabalho objetivou aprofundar o conhecimento sobre a mineralogia e as propriedades químicas de alguns desses solos, desenvolvidos de rochas sedimentares de distintas formações geológicas. Foram descritos e amostrados 5 (cinco) perfis de solo, sendo um Latossolo e quatro Cambissolos.  Na TFSA, foram feitas análises físicas (areia, silte, argila) e químicas de caracterização básica ( pH em água e sal, carbono orgânico, Ca, Mg, K, Na, Al, H+Al) e com base nesses parâmetros foi calculada a CTC efetiva, CTC pH7, Soma e Saturação por Bases. Análises mineralógicas foram conduzidas na fração argila do horizonte B de cada solo, utilizando-se difratometria de raios X. Todos os solos apresentaram reação muito ácida, com baixa soma e saturação por bases e teores elevados de carbono orgânico e Al trocável. A mineralogia da fração argila revelou predomínio de caulinitas em todos os solos, com quantidades consideráveis de illita, gibbsita e vermiculita com hidroxi-Al entrecamadas.

In the North Plateau of Santa Catarina state, Brazil, there is little information about the mineralogical composition of the soils and a few soil profiles were described and characterized in the region. The two generalized soil maps of Santa Catarina indicate predominance of Inceptisols, Entisols and Oxisols, with hydromorphic soils occupying areas of floodplains. These soils occur in relief from plane to strong wavy, where small and medium rural farmers develop diversified crops, with significant areas with pine reforestation. This work aimed to increase the knowledge of the mineralogical and chemical properties of some of these soils developed from sedimentary rocks of different geological formations. Five soil profiles were described and sampled, included one oxisol and four Inceptisols. In fine earth, physical (sand, silt, clay) and chemical analyzes were performed (pH in water, organic carbon, Ca2+, Mg, K, Na, Al, H + Al) and based on these attributes was calculated effective CEC, CEC at pH7, sum of bases and base saturation. Mineralogical analyzes were conducted in the clay fraction of the B horizon of each soil, using X-ray diffraction techniques. All soils showed very acid reaction, with low sum of bases and base saturation and high levels of organic carbon and exchangeable Al. The clay mineralogy revealed predominance of kaolinite in all soils, with considerable amounts of gibbsite, and vermiculite with hydroxy-Al interlayered.

Mineralogia da argila e propriedades químicas de solos do Planalto Norte Catarinense / Clay mineralogy and chemical properties of soils in the north plateau of Santa Catarina state

No Planalto Norte Catarinense são escassas as informações sobre a composição mineralógica dos solos e há poucos perfis de solo descritos e caracterizados para a região. O mapa de solos de Santa Catarina indica predominância de Cambissolos, Neossolos Litólicos e Latossolos, com Gleissolos ocupando áreas de várzeas. Esses solos ocorrem em relevo desde plano até forte ondulado, onde pequenos e médios proprietários rurais desenvolvem cultivos diversificados, com áreas expressivas de reflorestamentos com pinus. Este trabalho objetivou aprofundar o conhecimento sobre a mineralogia e as propriedades químicas de alguns desses solos, desenvolvidos de rochas sedimentares de distintas formações geológicas. Foram descritos e amostrados 5 (cinco) perfis de solo, sendo um Latossolo e quatro Cambissolos.  Na TFSA, foram feitas análises físicas (areia, silte, argila) e químicas de caracterização básica ( pH em água e sal, carbono orgânico, Ca, Mg, K, Na, Al, H+Al) e com base nesses parâmetros foi calculada a CTC efetiva, CTC pH7, Soma e Saturação por Bases. Análises mineralógicas foram conduzidas na fração argila do horizonte B de cada solo, utilizando-se difratometria de raios X. Todos os solos apresentaram reação muito ácida, com baixa soma e saturação por bases e teores elevados de carbono orgânico e Al trocável. A mineralogia da fração argila revelou predomínio de caulinitas em todos os solos, com quantidades consideráveis de illita, gibbsita e vermiculita com hidroxi-Al entrecamadas.(AU)

In the North Plateau of Santa Catarina state, Brazil, there is little information about the mineralogical composition of the soils and a few soil profiles were described and characterized in the region. The two generalized soil maps of Santa Catarina indicate predominance of Inceptisols, Entisols and Oxisols, with hydromorphic soils occupying areas of floodplains. These soils occur in relief from plane to strong wavy, where small and medium rural farmers develop diversified crops, with significant areas with pine reforestation. This work aimed to increase the knowledge of the mineralogical and chemical properties of some of these soils developed from sedimentary rocks of different geological formations. Five soil profiles were described and sampled, included one oxisol and four Inceptisols. In fine earth, physical (sand, silt, clay) and chemical analyzes were performed (pH in water, organic carbon, Ca2+, Mg, K, Na, Al, H + Al) and based on these attributes was calculated effective CEC, CEC at pH7, sum of bases and base saturation. Mineralogical analyzes were conducted in the clay fraction of the B horizon of each soil, using X-ray diffraction techniques. All soils showed very acid reaction, with low sum of bases and base saturation and high levels of organic carbon and exchangeable Al. The clay mineralogy revealed predominance of kaolinite in all soils, with considerable amounts of gibbsite, and vermiculite with hydroxy-Al interlayered.(AU)

Mineralogia e susceptibilidade magnética dos óxidos de ferro do horizonte B de solos do Estado do Paraná

Highly weathered tropical soils tend to accumulate iron and aluminum oxy-hydroxides. Among the iron oxy-hydroxides found in the clay fraction, goethite (Gt) and hematite (Hm) are the most abundant and studied. A smaller number of investigations have been publish to identify and to quantify maghemite (Mh), a ferrimagnetic mineral present in the clay size fraction of the soils, mainly in those developed from mafic rocks. Maghemite, along with magnetite (Mt) is responsible for the spontaneous magnetic behavior of the soils. This mineralogical attribute can be easy measured, in soils and sediments by mass magnetic susceptibility (LF), which magnitude is proportional to the concentration of ferrimagnetic minerals and it has been object of studies worldwide. The purpose of this research was to identify and quantify, by LF, the ferrimagnetic minerals of 32 samples from B-horizons of Paraná state soils. The mineral species present in the iron oxides concentrated clay size fractions were identified and semiquantified by x-rays diffraction (XRD). In this fraction the most abundant minerals are Gt and Hm. Maghemite was detected in 31 samples by LF and in only 17 samples by XRD. The LF values ranged from 16 to 8.077x10-8m³ kg-1 in the fine earth; from 12 to 7.953x10-8m³ kg-1 in clay fraction and from 0 to 18.737x10-8m³ kg-1 in clay fraction, after concentration of the iron oxides. The Mh of the soils presented an average value of 62.728x10-8m³ kg-1 and their presence in the X-rays diffractograms was only observed in samples with LF values above 1.000x10-8m³ kg-1.

Os solos tropicais altamente intemperizados tendem a acumular residualmente óxidos de ferro e alumínio. Entre os óxidos e hidróxidos de ferro presentes na fração argila, a goethita (Gt) e a hematita (Hm) são os mais abundantes e estudados. No entanto, há poucos estudos acerca da identificação e quantificação da maghemita (Mh), um mineral ferrimagnético que está na fração argila dos solos, principalmente naqueles desenvolvidos de rochas máficas. A Mh e a magnetita (Mt) são responsáveis pela magnetização espontânea dos solos. Esse atributo mineralógico pode ser medido nos solos e sedimentos pela susceptibilidade magnética por unidade de massa (BF), cuja magnitude é proporcional à concentração dos minerais ferrimagnéticos e é objeto de estudos em todo mundo. O objetivo deste trabalho foi identificar e quantificar, por BF, os minerais ferrimagnéticos de 32 amostras do horizonte B de solos do Estado do Paraná. As formas minerais presentes na fração argila concentrada de óxidos de ferro foram identificadas e semiquantificadas por difratometria de raios-X (DRX). Nessa fração, os minerais mais abundantes são a Gt e a Hm. A Mh foi detectada em 31 amostras por BF e em apenas 17 por DRX. Os valores de BF variaram de 16 a 8.077 na TFSA, de 12 a 7.953 na fração argila e de 0 a 18.737x10-8 m³ kg-1 na fração argila, após concentração dos óxidos de ferro. A Mh dos solos estudados apresentou valor médio de BF em 62.728x10-8m³ kg-1 e sua presença nos difratogramas de raios-X só foi verificada em amostras com valores de BF acima de 1.000x10-8m³ kg-1.

Mineralogia e susceptibilidade magnética dos óxidos de ferro do horizonte B de solos do Estado do Paraná

Highly weathered tropical soils tend to accumulate iron and aluminum oxy-hydroxides. Among the iron oxy-hydroxides found in the clay fraction, goethite (Gt) and hematite (Hm) are the most abundant and studied. A smaller number of investigations have been publish to identify and to quantify maghemite (Mh), a ferrimagnetic mineral present in the clay size fraction of the soils, mainly in those developed from mafic rocks. Maghemite, along with magnetite (Mt) is responsible for the spontaneous magnetic behavior of the soils. This mineralogical attribute can be easy measured, in soils and sediments by mass magnetic susceptibility (LF), which magnitude is proportional to the concentration of ferrimagnetic minerals and it has been object of studies worldwide. The purpose of this research was to identify and quantify, by LF, the ferrimagnetic minerals of 32 samples from B-horizons of Paraná state soils. The mineral species present in the iron oxides concentrated clay size fractions were identified and semiquantified by x-rays diffraction (XRD). In this fraction the most abundant minerals are Gt and Hm. Maghemite was detected in 31 samples by LF and in only 17 samples by XRD. The LF values ranged from 16 to 8.077x10-8m³ kg-1 in the fine earth; from 12 to 7.953x10-8m³ kg-1 in clay fraction and from 0 to 18.737x10-8m³ kg-1 in clay fraction, after concentration of the iron oxides. The Mh of the soils presented an average value of 62.728x10-8m³ kg-1 and their presence in the X-rays diffractograms was only observed in samples with LF values above 1.000x10-8m³ kg-1.

Os solos tropicais altamente intemperizados tendem a acumular residualmente óxidos de ferro e alumínio. Entre os óxidos e hidróxidos de ferro presentes na fração argila, a goethita (Gt) e a hematita (Hm) são os mais abundantes e estudados. No entanto, há poucos estudos acerca da identificação e quantificação da maghemita (Mh), um mineral ferrimagnético que está na fração argila dos solos, principalmente naqueles desenvolvidos de rochas máficas. A Mh e a magnetita (Mt) são responsáveis pela magnetização espontânea dos solos. Esse atributo mineralógico pode ser medido nos solos e sedimentos pela susceptibilidade magnética por unidade de massa (BF), cuja magnitude é proporcional à concentração dos minerais ferrimagnéticos e é objeto de estudos em todo mundo. O objetivo deste trabalho foi identificar e quantificar, por BF, os minerais ferrimagnéticos de 32 amostras do horizonte B de solos do Estado do Paraná. As formas minerais presentes na fração argila concentrada de óxidos de ferro foram identificadas e semiquantificadas por difratometria de raios-X (DRX). Nessa fração, os minerais mais abundantes são a Gt e a Hm. A Mh foi detectada em 31 amostras por BF e em apenas 17 por DRX. Os valores de BF variaram de 16 a 8.077 na TFSA, de 12 a 7.953 na fração argila e de 0 a 18.737x10-8 m³ kg-1 na fração argila, após concentração dos óxidos de ferro. A Mh dos solos estudados apresentou valor médio de BF em 62.728x10-8m³ kg-1 e sua presença nos difratogramas de raios-X só foi verificada em amostras com valores de BF acima de 1.000x10-8m³ kg-1.

Mineralogical characterization of a highly-weathered soil by the Rietveld Method

The mineralogical characterization through mineral quantification of Brazilian soils by X-ray diffraction data using the Rietveld Method is not common. A mineralogical quantification of an Acric Ferralsol from the Ponta Grossa region, state of Paraná, Brazil, was carried out using this Method with X-Ray Diffraction data to verify if this method was suitable for mineral quantification of a highly-weathered soil. The A, AB and B3 horizons were fractioned to separate the different particle sizes: clay, silt, fine sand (by Stokes Law) and coarse sand fractions (by sieving), with the procedure free of chemical treatments. X-ray Fluorescence, Inductively Coupled Plasma Atomic Emission Spectrometry, Infrared Spectroscopy and Mössbauer Spectroscopy were used in order to assist the mineral identification and quantification. The Rietveld Method enabled the quantification of the present minerals. In a general way, the quantitative mineralogical characterization by the Rietveld Method revealed that quartz, gibbsite, rutile, hematite, goethite, kaolinite and halloysite were present in the clay and silt fractions of all horizons. The silt fractions of the deeper horizons were different from the more superficial ones due to the presence of large amounts of quartz. The fine and the coarse sand fractions are constituted mainly by quartz. Therefore, a mineralogical quantification of the finer fraction (clay and silt) by the Rietveld Method was successful.

A caracterização mineralógica por meio da quantificação dos minerais presentes em solos brasileiros por difração de raios X usando o Método de Rietveld é, ainda, pouco comum. Neste trabalho foi realizada a quantificação mineralógica de um Latossolo Vermelho ácrico da região de Ponta Grossa, Paraná, Brasil, utilizando o Método de Rietveld com dados de Difração de Raios X e também verificado se o método foi adequado na quantificação mineral de um solo altamente intemperizado. Os horizontes A, AB e B3 foram separados fisicamente nas frações: argila, silte, areia fina (por meio da Lei de Stokes) e areia grossa (por peneiramento) sem qualquer tratamento químico. As técnicas de Fluorescência de raios X, Espectroscopia de Emissão Atômica com Fonte de Plasma Induzido, Espectroscopia de Infravermelho e Espectroscopia Mössbauer foram utilizadas para auxiliar na identificação e quantificação dos minerais. O Método de Rietveld possibilitou a quantificação dos minerais presentes nas frações argila e silte de todos os horizontes: quartzo, gibbsita, rutílio, hematita, goethita, caulinita e haloisita. Na fração silte os horizontes mais profundos são diferentes do mais superficial devido à presença de grandes quantidades de quartzo. As frações areia fina e grossa são constituídas principalmente de quartzo. Portanto, o Método de Rietveld foi adequado para quantificação dos minerais, principalmente, das frações mais finas (argila e silte).

Mineralogical characterization of a highly-weathered soil by the Rietveld Method

The mineralogical characterization through mineral quantification of Brazilian soils by X-ray diffraction data using the Rietveld Method is not common. A mineralogical quantification of an Acric Ferralsol from the Ponta Grossa region, state of Paraná, Brazil, was carried out using this Method with X-Ray Diffraction data to verify if this method was suitable for mineral quantification of a highly-weathered soil. The A, AB and B3 horizons were fractioned to separate the different particle sizes: clay, silt, fine sand (by Stokes Law) and coarse sand fractions (by sieving), with the procedure free of chemical treatments. X-ray Fluorescence, Inductively Coupled Plasma Atomic Emission Spectrometry, Infrared Spectroscopy and Mössbauer Spectroscopy were used in order to assist the mineral identification and quantification. The Rietveld Method enabled the quantification of the present minerals. In a general way, the quantitative mineralogical characterization by the Rietveld Method revealed that quartz, gibbsite, rutile, hematite, goethite, kaolinite and halloysite were present in the clay and silt fractions of all horizons. The silt fractions of the deeper horizons were different from the more superficial ones due to the presence of large amounts of quartz. The fine and the coarse sand fractions are constituted mainly by quartz. Therefore, a mineralogical quantification of the finer fraction (clay and silt) by the Rietveld Method was successful.

A caracterização mineralógica por meio da quantificação dos minerais presentes em solos brasileiros por difração de raios X usando o Método de Rietveld é, ainda, pouco comum. Neste trabalho foi realizada a quantificação mineralógica de um Latossolo Vermelho ácrico da região de Ponta Grossa, Paraná, Brasil, utilizando o Método de Rietveld com dados de Difração de Raios X e também verificado se o método foi adequado na quantificação mineral de um solo altamente intemperizado. Os horizontes A, AB e B3 foram separados fisicamente nas frações: argila, silte, areia fina (por meio da Lei de Stokes) e areia grossa (por peneiramento) sem qualquer tratamento químico. As técnicas de Fluorescência de raios X, Espectroscopia de Emissão Atômica com Fonte de Plasma Induzido, Espectroscopia de Infravermelho e Espectroscopia Mössbauer foram utilizadas para auxiliar na identificação e quantificação dos minerais. O Método de Rietveld possibilitou a quantificação dos minerais presentes nas frações argila e silte de todos os horizontes: quartzo, gibbsita, rutílio, hematita, goethita, caulinita e haloisita. Na fração silte os horizontes mais profundos são diferentes do mais superficial devido à presença de grandes quantidades de quartzo. As frações areia fina e grossa são constituídas principalmente de quartzo. Portanto, o Método de Rietveld foi adequado para quantificação dos minerais, principalmente, das frações mais finas (argila e silte).