Abstract
Fourier transform infrared (FTIR) spectroscopy is a widespread and useful technique for characterizing the chemical composition of soil/sediment organic matter (SOM). However, the mineral components of the samples limit spectral analysis since they mask SOM’s distinctive signals. Big efforts have been made in this matter to eliminate the spectral interferences of mineral constituents of the samples, by demineralization with hydrofluoric acid (DHF), or spectral subtraction. This work aimed to upgrade reported DHF methods and optimize a sample preparation methodology for SOM characterization by FTIR spectroscopy combining the potential of spectral and multivariate analysis. Semi-quantitative FTIR ratios were introduced as input variables for principal component analysis to determine the optimal DFH conditions to characterize SOM. One-way analysis of variance (ANOVA, α = 0.05) test revealed that the optimal demineralization was achieved with two cycles of HF 10% v/v at 60 °C, against five HF cycles and room temperature, previously reported. The DHF at the optimal conditions not only improved the demineralization efficiency against that of the reported methods but also did not cause significant undesirable modifications in SOM that could distort the FTIR analysis. These conclusions have statistical significance and are based on the qualitative information of the spectra and also on a comprehensive semi-quantitative study of them.
Graphic abstract
Article Highlights
-
Chemometric optimization of a demineralization method .
-
Spectral analysis and PCA for chemical characterization of sediment organic matter.
-
Semi-quantitative analysis of sediment organic matter by FTIR.
-
Exhaustive HF-demineralization for sediment organic matter analysis by FTIR.
-
The demineralization is efficient and does not significantly modify organic matter.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Abraham EDC, D’Angelo JA, Mammana SB et al (2019) Recycling control of histological xylol: a chemometric approach. ChemistrySelect 4:10856–10862. https://doi.org/10.1002/slct.201901659
Calderón FJ, Reeves JB, Collins HP, Paul EA (2011) Chemical differences in soil organic matter fractions determined by diffuse-reflectance mid-infrared spectroscopy. Soil Sci Soc Am J 75:568–579. https://doi.org/10.2136/sssaj2009.0375
Calderón F, Haddix M, Conant R et al (2013) Diffuse-reflectance Fourier-transform mid-infrared spectroscopy as a method of characterizing changes in soil organic matter. Soil Sci Soc Am J 77:1591–1600. https://doi.org/10.2136/sssaj2013.04.0131
Colthup NB, Daly LH, Wiberley SE (1964) Introduction to infrared and Raman spectroscopy, 1st edn. Academic Press, New York
Cuypers C, Grotenhuis T, Rulkens W et al (2002) Amorphous and condensed organic matter domains: the effect of persulfate oxidation on the composition of soil/sediment organic matter. Chemosphere 48:919–931. https://doi.org/10.1016/S0045-6535(02)00123-6
D’Angelo JA (2006) Analysis by Fourier transform infrared spectroscopy of Johnstonia (Corystospermales, Corystospermaceae) cuticles and compressions from the Triassic of Cacheuta, Mendoza, Argentina. Ameghiniana 43:669–685
D’Angelo J, Marchevsky E (2004) FT-IR determination of aliphatic and aromatic CH contents of fossil leaf compressions. Part 1: analysis, curve-resolving and choice of bands. Anu Latinoam Educ Química 17:37–41
D’Angelo JA, Zodrow EL (2016) 3D chemical map and a theoretical life model for Neuropteris ovata var. simonii (index fossil, Asturian, Late Pennsylvanian, Canada). Int J Coal Geol 153:12–27. https://doi.org/10.1016/j.coal.2015.11.007
D’Angelo JA, Zodrow EL (2018) Density and biomechanical properties of fossil fronds. A case study of Neuropteris ovata (seed fern, Late Pennsylvanian, Canada). Int J Coal Geol 198:63–76
Davies BE (1974) Loss-on-ignition as an estimate of soil organic matter. Soil Sci Soc Am J 38:150–151. https://doi.org/10.2136/sssaj1974.03615995003800010046x
Dick DP, Santos JHZ, Ferranti EM (2003) Chemical characterization and infrared spectroscopy of soil organic matter from two Southern Brazilian soils. Rev Bras Cienc do Solo 27:29–39
Fernández-Ugalde O, Barré P, Virto I et al (2016) Does phyllosilicate mineralogy explain organic matter stabilization in different particle-size fractions in a 19-year C3/C4 chronosequence in a temperate Cambisol? Geoderma 264:171–178. https://doi.org/10.1016/j.geoderma.2015.10.017
Gonçalves CN, Dalmolin RSD, Dick DP et al (2003) The effect of 10% HF treatment on the resolution of CPMAS 13C NMR spectra and on the quality of organic matter in Ferralsols. Geoderma 116:373–392. https://doi.org/10.1016/S0016-7061(03)00119-8
Kauppinen JK, Moffatt DJ, Mantsch HH, Cameron DG (1981) Fourier self-deconvolution: a method for resolving intrinsically overlapped bands. Appl Spectrosc 35:271–276
Kögel-Knabner I, Rumpel C (2018) Advances in molecular approaches for understanding soil organic matter composition, origin, and turnover: a historical overview, 1st edn. Elsevier Inc., Oxford
Lafuente Diaz MA, D’Angelo JA, Del Fueyo GM, Carrizo MA (2020) FTIR spectroscopic features of the pteridosperm Ruflorinia orlandoi and host rock (Springhill Formation, Lower Cretaceous, Argentina). J South Am Earth Sci 99:102520. https://doi.org/10.1016/j.jsames.2020.102520
Lana NB, Koch E, Angelo JAD et al (2014) Sediment physicochemical properties condition pollutant association: a multivariate study of polybrominated diphenyl ethers on the Mendoza River irrigation areas. Revista de la Facultad de Ciencias Agrarias 46:57–71
Lin R, Ritz GP (1993b) Studying individual macerals using i.r. microspectrometry, and implications on oil versus gas/condensate proneness and “low-rank” generation. Org Geochem 20:695–706. https://doi.org/10.1016/0146-6380(93)90055-G
Lin R, Ritz GP (1993a) Reflectance FT-IR microspectroscopy of fossil algae contained in organic-rich shales. Appl Spectrosc 47:265–271
Margenot AJ, Calderón FJ, Magrini KA, Evans RJ (2017) Application of DRIFTS, 13C NMR, and py-MBMS to characterize the effects of soil science oxidation assays on soil organic matter composition in a mollic xerofluvent. Appl Spectrosc 71:1506–1518. https://doi.org/10.1177/0003702817691776
Margenot AJ, Parikh SJ, Calderón FJ (2019) Improving infrared spectroscopy characterization of soil organic matter with spectral subtractions. J Vis Exp 2019:1–15. https://doi.org/10.3791/57464
Mastalerz M, Bustin RM (1997) Variation in the chemistry of macerals in coals of the Mist Mountain Formation, Elk Valley coalfield, British Columbia, Canada. Int J Coal Geol 33:43–59. https://doi.org/10.1016/S0166-5162(96)00003-1
Mastalerz M, Marc Bustin R (1993) Electron microprobe and micro-FTIR analyses applied to maceral chemistry. Int J Coal Geol 24:333–345. https://doi.org/10.1016/0166-5162(93)90018-6
Merlin N, Lima VA, Santos-Tonial LM (2015) Instrumental and experimental conditions for the application of Fourier transform infrared analysis on soil and humic acid samples, combined with chemometrics tools and scanning electron microscopy. J Braz Chem Soc 26:1920–1927
Miyazawa M, Pavan MA, de Oliveira EL et al (2000) Gravimetric determination of soil organic matter. Brazilian Arch Biol Technol 43:475–478. https://doi.org/10.1590/s1516-89132000000500005
Olivieri AC (2018) Introduction to multivariate calibration: a practical approach, 1st edn. Springer, Berlin
Orlov DS, Sadovnikova LK (2005) Soil organic matter and protective functions of humic substances in the biosphere BT. In: Perminova IV, Hatfield K, Hertkorn N (eds) Use of humic substances to remediate polluted environments: from theory to practice. Springer, Dordrecht, pp 37–52
Padilla JE, Calderón FJ, Acosta-Martinez V et al (2014) Diffuse-reflectance mid-infrared spectroscopy reveals chemical differences in soil organic matter carried in different size wind eroded sediments. Aeolian Res 15:193–201. https://doi.org/10.1016/j.aeolia.2014.06.003
Reeves JB (2012) Mid-infrared spectral interpretation of soils: is it practical or accurate? Geoderma 189–190:508–513. https://doi.org/10.1016/j.geoderma.2012.06.008
Rumpel C, Rabia N, Derenne S et al (2006) Alteration of soil organic matter following treatment with hydrofluoric acid (HF). Org Geochem 37:1437–1451. https://doi.org/10.1016/j.orggeochem.2006.07.001
Schmidt MWI, Knicker H, Hatcher PG, Kögel-Knabner I (1997) Improvement of 13C and 15N CPMAS NMR spectra of bulk soils, particle size fractions and organic material by treatment with 10% hydrofluoric acid. Eur J Soil Sci 48:319–328. https://doi.org/10.1111/j.1365-2389.1997.tb00552.x
Smith BC (2011) Fundamentals of fourier transform infrared spectroscopy, 2nd edn. CRC Press
Sobkowiak M, Painter P (1992) Determination of the aliphatic and aromatic CH contents of coals by FT-IR: studies of coal extracts. Fuel 71:1105–1125
Yeasmin S, Singh B, Johnston CT, Sparks DL (2017) Evaluation of pre-treatment procedures for improved interpretation of mid infrared spectra of soil organic matter. Geoderma 304:83–92. https://doi.org/10.1016/j.geoderma.2016.04.008
Zhang C, Xu W, Zhang Z et al (2017) Preparation of mullite whiskers from kaolin via the addition of tribasic calcium phosphate. Int J Appl Ceram Technol 14:1206–1212. https://doi.org/10.1111/ijac.12737
Zodrow EL, Mastalerz M (2001) Chemotaxonomy for naturally macerated tree-fern cuticles (Medullosales and Marattiales), Carboniferous Sydney and Mabou Sub-Basins, Nova Scotia, Canada. Int J Coal Geol 47:255–275. https://doi.org/10.1016/S0166-5162(01)00045-3
Zodrow EL, D’Angelo JA, Mastalerz M, Keefe D (2009) Compression-cuticle relationship of seed ferns: Insights from liquid-solid states FTIR (Late Palaeozoic-Early Mesozoic, Canada-Spain-Argentina). Int J Coal Geol 79:61–73. https://doi.org/10.1016/j.coal.2009.06.001
Zodrow EL, D’Angelo JA, Taylor WA et al (2016) Secretory organs: implications for lipoid taxonomy and kerogen formation (seed ferns, Pennsylvanian, Canada). Int J Coal Geol 167:184–200. https://doi.org/10.1016/j.coal.2016.10.004
Acknowledgements
We thank Dr. Nerina B. Lana (IANIGLA and FCEN-UNCuyo) for her collaboration in collecting the samples, which were considered in her Doctoral thesis (2012) and previous publication of this group (2014).
Funding
This work was supported by Consejo Nacional de Investigaciones Científicas y Técnicas (PIUE 22920160100091CO), Agencia Nacional de Promoción de la Investigación, el Desarrollo Tecnológico y la Innovación (PICT 2017: 1091), Universidad Nacional de Cuyo (06/M102 J.C.A. and 06/M106 J.A.D.), Program H2020-MSCA-RISE: INTERWASTE ID# 734522 and A. Research Office (W911NF-19-1-0423).
Author information
Authors and Affiliations
Contributions
The authors’ order represents the contribution degree in this work.
Corresponding author
Ethics declarations
Conflicts of interest
On behalf of all authors, the corresponding author states that there is no conflict of interest.
Human and animal rights and informed consent
The research presented did not involve human or animals participants.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Abraham, E.C., D’Angelo, J.A. & Altamirano, J.C. Chemometric Optimization of a Demineralization Method for Analysing Sediment Organic Matter by Fourier Transform Infrared Spectroscopy. Int J Environ Res 15, 645–654 (2021). https://doi.org/10.1007/s41742-021-00338-w
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s41742-021-00338-w