Photoacoustics 18 (2020) 100162

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Photoacoustics
journal homepage: www.elsevier.com/locate/pacs

FTIR photoacoustic spectroscopy for identification and assessment of soil T

components: Chernozems and their size fractions
Petr K. Krivosheina, Dmitry S. Volkova,b, Olga B. Rogovab, Mikhail A. Proskurnina,*
a
Chemistry Department, M.V. Lomonosov Moscow State University, Leninskie Gory, 1-3, GSP-1, Moscow, 119991, Russia
b
Department of Chemistry and Physical Chemistry of Soils, V.V. Dokuchaev Soil Science Institute, Pyzhevsky Per., 7/2, Moscow 119017, Russia

A R T I C LE I N FO A B S T R A C T

Keywords: FTIR photoacoustic spectroscopy was used to approach inorganic matrix components and organic-matter con-
FTIR photoacoustic spectroscopy stituents of chernozem size fractions (1–5000 μm, by dry sieving) with a different history of use (from intact
Attenuated total internal reflection FTIR steppe to permanent bare fallow, a continuous long-term field experiment). The conditions of FTIR photo-
spectroscopy acoustic measurements in continuous-scan modes were compared with attenuated total reflection measure-
Soil composition
ments, the advantages of photoacoustic measurements resulting from a higher intensity of the incident radiation
Chernozem
and signal-generating volume were discussed. Overtone peaks of quartz as a soil matrix component at
2000–1700 cm–1 were selected as a possible internal-standard (guide) bands for the comparison of photoacoustic
spectra. For different land-use samples, differences in the composition were found, which are differently man-
ifested in normalized spectra of size fractions, with millimeter-size, 20–100 μm, and silt fraction bearing the
maximum information.

1. Introduction identification of some of soil components (mainly mineral matrices like

carbonate, silicate, and clay minerals; SOM; or fertilizers) and research
IR spectroscopy has been used in soil research for a long time, but focused on plants and other objects [18,30–33]. The possibilities of PAS
over the last two decades its role has dramatically increased due to a for assessing the distribution of a substance over the depth of micro-
new technological level, advances in instrumental capabilities, new particles were considered for model particles [34] and soils [6].
modalities, and increased inherent sensitivity [1–5]. Interferometer- Quantitative FTIR-PAS measurements include the determination of soil
based FTIR photoacoustic spectroscopy (FTIR-PAS) proves to be a de- organic/inorganic carbon ratio [35], soil water content [36,37], and
veloped instrument for complex samples [6–10]. It can be used for carbonate contents in carbonate soils [17]. The distribution of the SOM
mineral, polymer, and technological samples, and is capable for the on depth layers of soil samples in long-term experiments was shown
measurements and modelling of the dependence of soil properties on its [16]. Due to the complex nature of FTIR-PAS information, the main-
physical and elemental composition, moisture, porosity, and density stream in data interpretation includes multivariate calibrations, and
[11–19]. generalized and self-adaptive models for integral soil parameters like
Apart from bulk soil properties, studies on the roles of agrogenesis total and exchangeable P, N, K and total carbon were proposed
and anthropogenesis on the changes in physical and physicochemical [13,15,18,38–40]. FTIR-PAS can be on demand for studies of changes of
properties of soils become more and more topical [20–22]. A new and properties of entities of different hierarchical levels under the action of
demanding level is the assessment of composition of soil fractions and agrogenesis and anthropogenesis [33,41].
structures including changes at meso- and microaggregate levels Thus, most of the applications of FTIR-PAS are focused on either
[23–26]. Solving these problems requires highly informative methods qualitative analysis of bands in soil samples or building the prediction
and approaches because soils are complex ensembles of inorganic ma- models for rather different soil type matrices or models for general soil
trices and soil organic matter (SOM) [27]. The latter itself is an orga- indicators [33]. As far as we are concerned, there are no studies in
nomineral continuum of high- and low-molecular organic and inorganic which FTIR-PAS spectroscopy is used for a more detailed molecular
substances in a finely dispersed state [28] and the largest solid carbon (structural) or functional analysis of soils.
reservoir [29]. Chernozems were selected for this study as test soil samples because
The most widespread applications of FTIR-PAS include the they belong to the most fertile soils and are a significant organic carbon

⁎
Corresponding author.
E-mail address: [email protected] (M.A. Proskurnin).

https://doi.org/10.1016/j.pacs.2020.100162
Received 5 December 2019; Received in revised form 12 January 2020; Accepted 19 January 2020
Available online 22 January 2020
2213-5979/ © 2020 The Authors. Published by Elsevier GmbH. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
P.K. Krivoshein, et al. Photoacoustics 18 (2020) 100162

source giving more than 400 tons of carbon per hectare [42,43]. They clamping screw.
also have a unique aggregate structure due to the peculiarities in
composition of organic matter. Due to heavy agricultural use, the 2.1.2. FTIR-PAS measurements
changes in chernozem SOM (both composition and the distribution) is a FTIR-PAS measurements were made using a PAC 300 photoacoustic
topical problem [44]. In the same time, the matrix of chernozems may detector accessory (MTEC Photoacoustics Inc., USA) for direct photo-
also change upon use, both in the fractional and aggregate properties. acoustic detection of optical absorption spectra of solids and semisolids
Thus, assessing and monitoring the physical, chemical, and the whole with IR Fourier spectrometers. The working principle of the detector is
structural composition of chernozems is a relevant problem. based on a single-dimensional heat transfer model, Fig. 1 [46–48]. The
The samples of Kursk chernozems from a continuous long-term field incident IR beam from the interferometer is focused from above on a
experiment were selected from intact steppe to permanent bare fallow horizontally located sample placed in a closed environment filled with a
and represent different land uses. They have a silicate matrix and no working gas with a limited volume. The IR beam is absorbed by the
significant amounts of carbonate (no soil effervescence after applying upper layers of the solid sample depending on its absorption coefficient
10% HCl), sulfate, and phosphate species [45]. In the previous appli- and converted into heat. The temperature modulations depend on the
cations of FTIR-PAS, chernozems were not studied by this method in interferometer modulation frequency, absorption coefficient at given
detail, though it was found that water-extractable organic carbon wavelengths, and thermal diffusivity of the sample. Produced inter-
contents shows a definite positive correlation to the IR absorbance at ferometer-modulated thermal waves from the volume limited by the
2920 cm−1 assigned to CHe vibrations and this correlation increased thermal diffusion depth (thermal-wave decay length, Fig. 1a) or ra-
with the probing depth at a micrometer scale [6]. However, no detailed diation-absorption depth (Fig. 1b) are transferred into the working gas;
information on FTIR-PAS measurements is presented so far. the direction of this one-dimensional heat flow is considered opposite to
Thus, the aim of this study is to work out the approaches for the the direction of the incident beam [46–48]. Thermal waves generate
identification and assessment of inorganic components and organic- pressure (acoustic) waves in the working gas that are detected with a
matter components of bulk samples and size fractions (by dry sieving) microphone located near the main axis of the FTIR-PAS instrument. The
of chernozems as SiO2-based SOM-rich soils with different type of land reflection losses of the incident beam on the sample surface are con-
use by FTIR-PAS. sidered negligible. The lower (rear) sample surface is thermally
grounded and optically non-reflective.
This accessory mounts in the standard baseplate of a Bruker spec-
2. Materials and methods trometer inside the spectrometer sample compartment for vibration
isolation. The PAC 300 sample chamber is purged with helium gas in
2.1. Instruments order to increase the heat transfer from the solid sample to the working
gas and provide the maximum signal generation (over a factor of 3
2.1.1. FTIR measurements compared to air) [46]. The IR beam from the interferometer is focused
IR spectra were recorded on a Vertex 70 and a Vertex 70 V single- to a diameter of 5 mm onto the sample surface (http://www.mtecpas.
beam IR Fourier spectrometers (Bruker Optik GmbH, Germany) com). PAS 300 microphone sensitivity id 50 mV/Pa.
equipped with a He-Ne laser as a calibration line, a standard KBr and a Samples prepared according to the procedure described below
wide-range silicon beamsplitters, and wide-range DTGS detectors. (Section 2.2) were placed into a stainless-steel sample cup (diameter,
Bruker OPUS 7.5 software was used for signal acquisition and proces- 10 mm; depth, 3 mm) without significant pressing or compacting
sing. (Fig. 2a), the amount of sample was selected so that the flattened upper
In attenuated total reflection (ATR) measurements, a GladiATR surface is approximately 1 mm below the brass cup holder rim to ensure
single-reflection attenuated total internal reflection accessory with a the minimum working gas volume to increase the detection sensitivity.
diamond crystal (incident angle 45°; Pike Technologies, USA) and a The test sample was put in the nest of the cup holder, which was put
wide-range silicon beamsplitter was used. The background signal was and sealed in the PAC 300 accessory (http://www.mtecpas.com). The
recorded prior each sample. The acquisition parameters of ATR spectra cell compartment was purged with helium for 5–10 s; next, the helium
are shown in Table 1; ATR correction was made using the value of flow was stopped, and the spectrum was measured. Before each FTIR-
sample refractive index of 1.33. Samples of 5–10 mg were transferred in PAS measurement, the background (reference) spectrum (Fig. 3) was
a dry state to the crystal of the ATR accessory and then clamped with a recorded using a highly pure compressed graphite (carbon black)
standard reference sample from MTEC Photoacoustics Inc. (Fig. 2b).
Table 1
Except for slow-scan measurements (see below), where single sample
Measurement conditions for FTIR-PAS and ATR-FTIR.
measurements were made (due to significant time required for a single
Parameter FTIR-PAS ATR-FTIR measurement), in all other cases, the data were obtained for three re-
–1
plicate measurements and averaged after the whole data post-proces-
Spectral range, cm 6000–300 or 4000–400
Wavenumber resolution, cm–1 8 2 sing described below (Sections 2.1.2–2.1.4).
Number of background acquisition 64–256 64 The parameters for recording FTIR-PAS spectra are summed up in
scans Table 1. FTIR-PAS spectra were obtained in continuous-scan modes, by
Number of sample acquisition scans 64–256 64 varying the interferometer modulation frequency (rapid-scan modes of
Phase resolution 10 16
10.0, 7.5, 2.5, and 1.6 kHz and slow-scan modes of 250 and 150 Hz at
Phase correction mode Mertz or manual (see the Mertz
text) the reference He–Ne line of the FTIR spectrometer), which correspond
Apodization function Blackman–Harris, three-term to the optical path difference (OPD) velocities of 0.0095, 0.158, 0.101,
Zero filling 2 0.158, 0,475, and 0.633 cm/s, respectively. The number of scans for a
Aperture, mm 8
sample and background are: at frequencies of 150 Hz – 1.6 kHz, 64 and
Interferometer modulation frequency, 150, 250, 1600, 2500, 7500, 10000
Hz 10000 at 7.5–10.0 kHz, 256. The aperture of the FTIR spectrometer was set
Background acquisition preamplifier Automatic fully open. In each experiment, the preamplifier gain was set to provide
gain the centerburst interferogram amplitude of several volts but without
Sample acquisition preamplifier gain Automatic preamplifier clipping to provide the work of the AD converter of FTIR
Pre-amplification Ref
spectrometers [46]; the gain was set independently for the reference
Source MIR
Beam splitter KBr or wide MIR-FIR (Si) and sample measurements.
For all the samples, the whole information package—reference

2
P.K. Krivoshein, et al. Photoacoustics 18 (2020) 100162

Fig. 1. The representation of the principle of signal generation

in FTIR-PAS measurements in a single-dimension signal gen-
eration for (a) a sample with thermal-diffusion limited signal
generation and (b) a sample with radiation-penetration lim-
ited signal generation (optical saturation). In both cases, for
clarity sake, thermal-wave generated zones in the samples
(denoted as red-to-orange) are not shown at edges to reveal
the IR absorption gradients (yellow-to-brown). In both cases,
optical and thermal penetration depths are shallower than the
sample thickness, and the sample mount is non-reflective and
thermally ground.

environmental CO2 and H2O was not used during acquisition and ap-
plied at this point. The insignificant effect of the water vapor con-
tribution in the range 2000–1200 cm–1 was checked by the measure-
ments of the reference material, poly(propylene), see Supplementary
information, Fig. S1, and the acquisition of the reference-divided
spectra of carbon black vs. carbon black by the software (Fig. 3, red
line).

2.1.3. Data phase correction

For all FTIR-PAS measurements, the phase spectra for the reference
and sample were were checked (the phase spectrum for the reference
was either calculated from the interferogram or used explicitly in
carbon black vs. carbon black sample measurement). If the phase
spectrum of the reference was below or in the crossing position with the
sample spectrum, the reference interferogram was shifted by 1 or 2
points according to [49] to obtain a reference phase spectrum com-
pletely above the sample phase spectrum. From this data, the new
amplitude single-channel spectra and the resulting FTIR-PAS reference-
divided spectrum were rebuilt manually with environmental correction
by Bruker OPUS 7.5 software to account for water vapor contribution.
Fig. 2. (a) a soil sample and (b) reference sample of carbon black (MTEC In most cases, when relative positions of the phase spectra were correct,
Photoacoustics Inc.) in a stainless-steel cup mounted in sample holders.
no manual reconstruction was done, and the spectra obtained by de-
fault Mertz phase correction provided by Bruker OPUS 7.5 software
interferogram and single-channel reference amplitude spectrum, were used instead.
sample interferogram, phase spectrum, and single-channel sample am-
plitude spectrum—were stored. The final reference-divided PAS spec-
2.1.4. Post-measurement data processing
trum was automatically calculated by point by point division of the
Spectra are always smoothed and wavenumber-corrected; in the
single-channel sample spectrum to the single-channel reference spec-
case of quantitative estimations they were background-corrected and
trum by Bruker OPUS 7.5 software. Software correction of the peaks of
normalized by the range selected as an internal-standard band (quartz,

Fig. 3. Full single-channel reference spectrum of carbon black

from MTEC Photoacoustics Inc. (black curve) used for division-
corrected FTIR-PAS spectra of soils (interferometer modulation
frequency, 250 Hz) and the reference/reference division spectrum
produced using the same reference as a test sample after proces-
sing (red curve). For visibility sake, the reference/reference
spectrum is shifted up from the zero position by a factor of 0.05.

3
P.K. Krivoshein, et al. Photoacoustics 18 (2020) 100162

see below). Initially, all ATR-FTIR and FTIR-PAS spectra were processed samples are given elsewhere [53]. Samples were taken on the site of a
using built-in functions of Bruker OPUS 7.5 software. FTIR-PAS spectra long-term field experiment of Kursk Research Institute of Agricultural
were smoothed out by 9–25 points; ATR-FTIR spectra, by 9–17 points. Production and the Streletskaya steppe of the V.V. Alekhin Tsentralno-
As carbon black was used as a reference, FTIR-PAS spectra were cor- Chernozemny Nature Reserve [54]. Soil granulometric composition is a
rected by multiplication by ∼ ν , where ∼ν is the wavenumber to balance heavy silty clay loamy texture. Main components are quartz, 35–40 %;
the intensities in the shortwave range, according to [48]. illites, 12–15 %; smectites, 12–15 %; and total organic carbon, 4–6 %.
For peak identification, the automatic peak picking function of The humus horizon (A + AB1) is 105–130 cm. Soil effervescence after
Bruker OPUS 7.5 software was used; for shoulder and weak peaks, si- applying 10% HCl starts from a depth of 65–70 cm. The density of the
milar automatic peak picking was used on first and second-derivative arable layer (0–30 cm) varies from 1.20 to 1.25 g/cm3 [45]. For com-
spectra, respectively; derivative spectra were produced by Bruker OPUS parison with soils, model samples of pure quartz sand (fraction
7.5 software. 10–50 μm) and silica gel were used.
To compare peak intensities for various size fractions and probing General soil samples (4–5 kg), in triplicate, were taken in 2017 at
depths, peak areas were used. Peak integration was made by Method A sites with a radius of 5 m using an envelope method according to GOST
(integration between peak boundaries without baseline subtraction 17.4.4.02-2017 Russian State Standard, the sampling depth is 0–10 cm
[here, methods are named according to Bruker OPUS 7.5]) for soil (topsoil). General samples were dried for two weeks in air, then stored
matrix range 1300–300 cm–1; by Method D (partial integration of at room temperature. An average sample of 0.5 kg was taken from the
overlapping peaks with double-side straight-line-regression baseline corresponding general sample, crushed, and sieved through a 1 mm
correction) in the overtone range 2500–1300 cm–1, and by Method F sieve.
(full integration of sharp peaks over broader peaks with double-side Fractionation of the average samples was carried out on an AS 200
polynomial-regression baseline correction) for the shortwave range sieving machine (Retsch GmbH) with a dry sieving holder and a set of
6000–2500 cm–1). precision sieves with a stainless steel mesh, 200 mm in diameter and
Baseline correction for the whole spectra was not applied due to the square mesh sizes of 50, 63, 71, 80, 90, 100, 250, and 500 μm, and 1, 2,
complex nature of the spectrum and no means to account for the band and 5 mm (Retsch GmbH). Ultramicro sieves with a diameter of
of water in 1000–500 cm–1 [50]; for certain parts of the spectra, auto- 200 mm and square cells of 20, 30, and 40 μm (Precision Eforming LLC,
matic concave rubber-band baseline correction was used separately in USA) were used to obtain fine fractions. Dry sieving procedure con-
the ranges corresponding to ranges indicated in the previous paragraph. sisted in sieving the whole sample (ca. 300 g) on a 5000, 2000, 1000,
FTIR-PAS spectra normalization was made by manually selecting 500, 250, 100, and 50 μm sieve column. Then, a fraction of 50–100 μm
the normalization range in Bruker OPUS 7.5 software, the range was no (ca. 10–30 g) was processed on a column with 90, 80, 71, and 63 μm
wider than 500 cm–1. Built-in vector normalization protocol was used. sieves. The obtained fraction below 50 μm (ca. 1–20 g) was sieved
For quantitative estimation, the data were normalized using appro- through a column of 40, 30, and 20 μm sieves. The sieving time on each
priate band ranges: 3700–3600 cm–1 (aluminosilicate peaks) for of three stages was 15 min (paused for a short time each minute) at a
6000–2500 cm–1; 2000–1750 cm–1 (quartz combination bands) for the sieving amplitude of 3 mm. Thus, soil fractions with particle sizes below
overtone range 2500–1300 cm–1, and 800–700 cm–1 (quartz lattice 20, 20–30, 30–40, 40–50, 50–63, 63–71, 71–80, 80–90, 90–100,
bands) for the matrix range 1300–300 cm–1. Overtone SiO2 bands of 100–250, 250–500, 500–1000, 1000–2000, 2000–5000, and above
2052–1924, 1924–1836, and 1832–1751 cm–1 were used as internal 5000 μm were obtained.
standards for comparing various land use types. The integral intensities Silt soil fractions (below 1.0 μm) were isolated by Shaimukhametov
of selected bands (3050–2800, 1712–1570, 1540–1515, 1480–1440, modification of the elutriation method [55,56]: the sample is exposed
1420–1365, 1350–1315, and 1310–1225 cm–1) were divided by the to ultrasound (UltraSonic, power 75%, 22 min) and then the particles
peak area of one of the internal standards. are separated to < 0.2 and 0.2–1.0 μm fractions on an Eppendorf 5910R
In SOM annealing experiments (Section 2.2), FTIR-PAS spectra of centrifuge. The remainder of the soil after the sludge separation was
initial (unheated) and processed (heated) samples were exported to divided into 1.0–2.0; 2.0–5.0; 5.0–10.0, 10.0–50.0, and > 50 μm frac-
Excel spreadsheet software, corrected, and normalized as above, and tions by sedimentation according to [56], the conditions were calcu-
the difference spectra were built. Due to different matrix absorptions, lated by the Stokes equation.
the spectra were processed by subranges and then manually reunited. To remove the organic constituents of the fractionated samples,
The profiling depths of specific absorption bands at a wavenumber annealing in air was performed for 3 h at a temperature of 525 °C in a
∼
ν under different modulation frequencies were estimated using the SNOL 10/900 shaft high-temperature electric laboratory furnace (AB
thermal-diffusion length μs ( ∼ ν ) = DT / πf ( ∼ν ) , where DT is sample Umega Group, Lithuania).
∼
thermal diffusivity and f ( ν ) is the modulation frequency at the wa-
venumber ∼ ν [48]. The values of f ( ∼ ν ) were calculated from OPD ve- 3. Results and discussion
locities as f ( ∼
ν ) = OPD∙ ∼ν . The values of thermal diffusivity of quartz
were taken from [51]. The values for thermal diffusivities of cherno- 3.1. Band assignment and modality comparison
zems were taken from the previous findings on chernozem by photo-
thermal-beam deflection measurements [52]. FTIR-PAS measurements of chernozems show rather distinct IR
To achieve comparable intensities in ATR-FTIR, all values of the spectra with many features (Fig. 4 and 5) resembling previous data on
ATR spectra were corrected (I0 + a) × b = Icorr , where I0 is the regis- chernozems obtained by other infrared modalities [57,58]. For all the
tered intensity, a is the coefficient lying in the interval 0.02–0.005; b is studied samples, FTIR-PAS spectra show good precision of the mea-
the coefficient in the interval 20–35; and Icorr is the intensity after the surements of the replicate portions of the same sample. The procedure
correction. of manual correction of the reference interferogram [49] (Section 2.1.3)
provided extra account for PAS spectra difference due to reference in-
2.2. Samples terferogram changes. As a result, high reproducibility of spectra of re-
plicate measurements of the same sample was achieved: the relative
Typical (Haplic) chernozems (Loamic, Pachic) from the Kursk re- standard deviation was as low as 0.05–0.07 for the range of
gion (Russia) with a significantly different history and intensity of land 4000–1000 cm–1.
use: native (intact) steppe vegetation, shelterbelt since 1964, cropland It is claimed that mid-IR absorbance bands of soil samples asso-
under wheat cultivated without rotation since 1964, and permanent ciated with characteristic soil attributes drop into three regions:
bare fallow since 1964 were selected for the study. The details on these 4000–2000, 2000–1400, and 1200–500 cm−1 [11], corresponding to

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P.K. Krivoshein, et al. Photoacoustics 18 (2020) 100162

Fig. 4. Photoacoustic (red) spectrum (Bruker Vertex 70 V, 250 Hz)

of a permanent-fallow sample of Kursk chernozem, fraction
30–40 μm. ATR (black) spectrum for the same sample is given for
comparison of relative intensities of bands and manually scaled to
the same scale as the photoacoustic spectrum. Photoacoustic
measurement parameters: resolution, 8 cm–1; 128 scans; pre-
amplifier gain, ×200 (position 7) for the reference and ×2000
(position 10) for the sample. Ranges of FTIR-PAS spectrum are
discussed in the text. Spectra are smoothed, wavenumber-cor-
rected, not background-corrected, and not normalized.

hydrogen-bond region, organic matter region, and inorganic soil ma- due to low signal-to-noise ratio of the reference-division spectra to
trix, respectively. The authors of [59] used individual databases for make any conclusions. The range 3700–2700 cm–1 is clearly dominated
interpreting peaks in FTIR-PAS spectra, although this interpretation by O-H stretching vibrations mainly from adsorbed water, and this band
showed peak assignment as organic or inorganic only without possible is clearly deconvoluted into two comparable contributions centered at
overlapping of different compounds. In our opinion, this picture is too 3490 and 3260 cm–1 from asynchronous and synchronous stretching
simplified, because the inorganic part of the soil is more sophisticated vibrations of water [50]. Rather intense sharp bands at 3730–3650 cm–1
and manifests itself in the whole region. According to [60], the mid-IR can be attributed to metal-bonded O-H in clay minerals [15] and illites
range of such complex organomineral samples can be divided into three and smectites, 3730, 3700, and 3630 cm–1 [61]. It is important that
main parts (Fig. 4): matrix fingerprint region 1100–500 cm−1, over- very sharp peaks at 3730 and 3700 cm–1 are not clearly seen in ATR
tone-combination band region 2500–1200 cm−1, and OH-region, spectra (see below).
4000–2500 cm−1. We believe that this region division better suits the On the shortwave shoulder of the broad OH peak, two peaks of C-H
studied soil samples. stretching vibrations at 2930 (asymmetric) and 2840 cm–1 (symmetric)
As the selected soil type, chernozems and their size fractions, are are seen that are usually attributed to SOM. However, this range is also
free from calcium carbonate, phosphates, and sulfates at the level they known to have complex high-level vibrations of amorphous SiO2 and
can affect mid-IR spectra, we excluded their bands from the con- quartz species [60,62,63]. Still, the shape and relative positions of these
sideration. Matrix minerals are composed mainly on quartz species and peaks is rather from SOM, which was previously confirmed in various
hydrosilicate minerals —illites, and smectites—as well as clay minerals cases of soil FTIR analysis [35,38,57,58]. It is worth mentioning here
with due percentage of amorphous silicon dioxide or hydrosilicate that these peaks are clearly seen in slow-scan modes of FTIR-PAS
species. Due to extreme complexity of soil samples and rather non-de- (Fig. 6) and almost disappear in rapid-scan modes at 7.5 kHz or higher.
tailed assignments in the literature, we summed up all the possible The region 2500–2000 cm–1 does not show any peaks except for the
entries in an assignment table (Table 2) giving both counterparts of atmospheric CO2 doublet; the only exception are low-intensity peaks at
possible target bands, inorganic matrix components and possible 2230 and 2140 cm–1, which most probably should be assigned to the
overlapping SOM constituents. For convenience sake, the three regions second overtone and combination of SiO2 vibrations of 1153 and
stated above are separated by horizontal lines in Table 2. 1070 cm–1 [60,63]. These bands start the range that is dominated by
FTIR-PAS spectra in the NIR region (5300–3800 cm–1) are too noisy overtone and combination bands of SiO2 peaks.

Fig. 5. Photoacoustic spectra of cropland samples of Kursk

chernozem, various fractions (Bruker Vertex 70, inter-
ferometer modulation frequency, 7.5 kHz): less than 20 μm
(red); 20–30 μm (orange); 50–63 μm (light green); 63–71 μm
(light cyan); 80–90 μm (green); 100–250 μm (teal);
250–500 μm (bright blue); 0.5–1 mm (dark blue); 1–2 mm
(magenta); 2–5 mm (brown); and over 5 mm (black). pre-
amplifier gain, ×200 (position 7) for the reference and
×2000 (position 10) for the sample. Spectra are smoothed,
wavenumber-corrected, not background-corrected, and not
normalized.

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P.K. Krivoshein, et al. Photoacoustics 18 (2020) 100162

Table 2
Band assignments for chernozem soils and their fractions. Three main ranges are separated with horizontal lines.
Band, cm–1 Inorganic (matrix) constituent Organic constituent PAS ATR

5300 Water, combination band v1 + v2 + v3 n/a Weak Absent

3730 Si–OH stretching (kaolinite, clay) n/a Shoulder Absent
3700 Si–OH stretching, tilted (kaolinite, clay) n/a Medium Absent
3620 Al(Mg)Si–OH stretching, straight n/a Intense Medium
3600–2600 Water, stretching, comprised of: N–H stretching Intense, broad Medium
3490 asynchronous v3 O–H, phenolic, alcohol, carboxylic
3270 synchronous, v1 O–H, phenolic, alcohol, carboxylic
2940–2860 (?) SiO2 overtone, complex overtone-combination bands C–H aliphatic chains, stretching Medium to weak, Weak
broad
2260–2220 SiO2 overtone ≅ 2 × 1095 n/a Weak Negative, Artefact
2140 SiO2 overtone ≅ 2 × 1070 n/a Weak Negative, Artefact
2030 SiO2 combination band ≅1000 + 1037 C–H aromatic bending overtone Shoulder Absent
2000 SiO2 overtone ≅ 2 × 1000 C=O stretching Medium Negative, Artefact
1970 SiO2 combination band ≅920 + 1037 or 970 + 1000 [60] C=O stretching shoulder Negative, Artefact
1950 SiO2 combination band ≅960 + 1000 C=O stretching shoulder Weak
1880–1866 SiO2 combination band ≅697 + 1163 C=O stretching Intense Weak
1783 SiO2 combination band ≅697 + 1072 C=O stretching Intense Weak
1710–1680 SiO2 combination band ≅760 + 920 N–H bending, amine; alkene –C=C– stretching, Weak shoulder Absent
1650–1640 water, bending v2, absorbed amide I, aromatic –C=C– stretching [16] Intense, sharp Medium
1620–1610 SiO2 overtone ≅2 × 795 C=O stretching Intense Intense
1540–1515 SiO2 combination band 450 + 1070 [71] amide II, aromatic rings, carboxyl C Shoulder Absent
1460 SiO2 amorphous, combination band ≅ 350 + 1153 O–H, C–H bending Shoulder Absent
1420 Mg–OH stretching [60] C–O stretching Shoulder Weak, shoulder
1380 SiO2 amorphous or SiO2 overtone ≅ 2 × 697 or O-H (coordinated bonded water) Intense Absent
combination band ≅350 + 1000 [60]
1260 SiO2 combination band ≅450 + 795 amide III, C–O stretch of aromatic rings and carboxylic Medium shoulder Absent
acids [38], C–O stretching
1230 Combination band SiO2 ≅ 470 + 760; silicates amide III, C–O stretch of aromatic rings and carboxylic Shoulder Absent
acids
1175 Combination band SiO2 ≅305 + 964 or ≅450 + 697 [60], n/a Medium, shoulder Absent
amorphous silica [86]
1153 Lattice SiO2 n/a Medium Medium
1095 SiO2, silicate Si–O stretching [86] cellulose Medium, shoulder Medium
1070 Lattice SiO2, Si–O stretching (kaolinite, illite) n/a Intense Intense
1037 Silicate Si–O stretching (kaolinite, illite) carbohydrates Intense, shoulder Intense
1000 SiO2 Si–O stretching lattice n/a Intense, shoulder Intense
975 SiO2 silicate Si–O stretching (kaolinite, illite) [86] n/a Intense, shoulder Intense
930–910 Silicate, alumosilicate overtone SiO2 ≅2 × 450 n/a Shoulder Absent
860 Al–OH (clay minerals) n/a Weak, shoulder Absent
830 Al–OH (clay minerals), smectite and illite [61] cellulose Weak Weak
796 SiO2 lattice stretching SiO2 silicate [86] C–H bending (non-aromatic) Intense Medium
774 Mg–OH, Al–OH (clay minerals) n/a Intense Intense
750 Mg–OH, Al–OH (clay minerals) n/a Weak shoulder Intense
720–690 Water, librations C–H bending (aromatic) Shoulder Absent
697 SiO2 Si–O–Si bending, lattice n/a Intense Intense
655 Silicate Si–O–Si bending, iron oxide n/a Medium Intense
513 SiO2 silicate O–Si–O bending n/a Shoulder Intense
490 SiO2 O–Si–O bending n/a Shoulder Intense
470 SiO2 O–Si–O bending [86] n/a Weak Intense
450 SiO2 O–Si–O bending lattice n/a Intense Intense
430–420 Mg-OH, Al–OH (clay minerals) n/a Shoulder Intense
400–395 SiO2 O–Si–O bending lattice; water, librations n/a Intense Intense
370–365 R(SiO4) [60]; amorphous silica [86] n/a Medium Intense
350 SiO2 n/a Medium Intense
330 (?) Mg–O stretching [60] n/a Medium Intense
318 Mg–O stretching n/a Medium Intense

The region 2050–1750 cm–1 has some distinct peaks, which are bands in negligible. These peaks manifested themselves only for frac-
claimed to be the manifestation of C]O stretching vibrations of various tions of large sizes, for silt fractions all these peaks are negligible
oxidized moieties of chernozem SOM and are consistent with the data (Fig. 5), which agrees with low contents of crystalline minerals in silt
from isolated humic substances [64,65]. However, this range is known soil fractions.
to contain rather strong combination bands of lattice vibrations of A medium-to-weak and relatively broad peak can be found by de-
697 cm–1 in quartz [60,62,66]. All the samples (except for silt fractions) convolution in 1710–1680 cm–1 of the shortwave shoulder of the in-
show a very characteristic triplet of well-defined, intense, and nearly tense broad peak centered at 1620 cm–1. This peak can be assigned as
overlapping peaks at 1990, 1870 (the highest intensity), and 1780 cm–1. C]C stretching of aromatic components of SOM [57] and has no dis-
Deconvolution shows that these peaks are mainly unimodal; for slow tinct counterparts of inorganic matrix components. Still, the intensity of
scan-modes, each peak in this triplet is in fact unresolved doublets of this peak is very low, and it can be used for detecting some extra ab-
similar parameters, which may be the manifestation of nearly equal sorption, and no quantitative approaches without sample preparation
quartz and illite/smectite contributions [61]. Annealing experiments were able under the conditions of the experiments.
(see below, Section 3.4) do not show a change in the parameters of Bands at 1650–1580 cm–1 are primarily associated with soil water
these peaks, so it can be concluded that SOM contributions to these and silicon dioxide [35]. The intense rather wide peak at

6
P.K. Krivoshein, et al. Photoacoustics 18 (2020) 100162

Fig. 6. Permanent fallow sample of Kursk chernozem, fraction

30–40 μm, at various interferometer modulation frequencies,
150 Hz (magenta), 250 Hz (blue), 1.6 kHz (green), 2.5 kHz
(orange), and 10 kHz (red); instruments are Bruker Vertex
70 V for for 150 and 250 Hz and Bruker Vertex 70 for kilohertz
frequencies; reference and sample preamplifier gain vary.
Photoacoustic measurement parameters: resolution, 8 cm–1;
128 scans. Spectra are smoothed, wavenumber-corrected, not
background-corrected, and not normalized.

1620–1615 cm–1 is composite and seems to be a combination of two is observed, while overtone and combination regions are poor due to no
peaks at 1640 and 1600 cm–1 corresponding to main bending vibrations significant contributions from the silicate lattice.
of absorbed water [50] and one of the main overtone bands in quartz Despite the saturation effects, all major quartz and hydrosilicate
and silica (Table 2), respectively. bands are distinguishable. The band at 1020–950 cm–1 is attributed to
The long-wave shoulder of this peak at 1600–1580 cm–1 is another SiOe stretching from both quartz and clay minerals, with the bands at
region with possible non-matrix contribution, and it was previously 950–600 cm–1 dominated by the vibration of (Mg,Al)−OH in clay mi-
used for nitrate species in soils [38]. However, in our opinion, apart nerals at 915 cm–1, iron oxides at 700–600 cm–1 together with possible
from large contributions from water and silicates, it corresponds to the contributions from aromatic and amine vibrations [15] are clearly seen.
strong absorption band of black carbon [67] used as a FTIR-PAS re- A low-intensity, but very stable peak at 830 cm–1 may be attributed to
ference (Fig. 3), so distortions in possible contributions are unavoid- illite and smectite minerals [61].
able. Finally, the secondary peaks appear centered at 1530 cm–1, which To sum up, the analysis of the spectra and band assignment shows
is another overtone band of quartz [62]. Thus, the region that in the whole region the spectra of chernozem soils are dominated
1600–1500 cm–1 is disadvantageous for quantification with FTIR-PAS with the quartz/hydrosilicate matrix and soil water, so these should be
unless another reference sample is used. main targets for assessment from IR spectra. Contrary to some previous
The region of 1450–1220 cm–1 also shows well defined medium- findings, SOM components cannot be assessed directly without some
intensity peaks that are attributed to overtones and combination bands chemical or thermal sampling or without further spectra processing.
of bending vibrations in quartz and hydrosilicates, especially 1390, As far as we are concerned, a full comparison of PAS, DRIFT and
1270, and 1240 cm–1 (Table 2). According to existing DRIFT measure- ATR features for soils was not done, although some advantages char-
ments, main bands in typical soils are CHe bending vibrations in- acteristic to PAS like depth profiling are shown [10,48,70]. Within the
cluding aliphatic and aromatic CHe (1300–1500 cm–1) and COe frames of this study, we intended to compare the spectral information
stretching vibrations from carbonates (1400–1500 cm–1); however, no provided by PAS and ATR modalities for the same samples. These
control over possible inorganic constituents was done [58,68]. The modalities are somewhat complementary (Fig. 4). From the viewpoint
band at 1400 cm–1 varying in different soil types is attributed to NOe of CH vibrations at 2900–2800 cm–1 region, the sensitivity of ATR and
contributions [38]. Thus, in our opinion, this region cannot be used for PAS modalities are the same, and the advantage of PAS is the depth
SOM quantification. probing only. For inorganic components, ATR provides more resolved
A small series or peaks between main and overtone ranges of quartz structural modes of the main lattice vibrations of the matrix in
at 1200 and 1190 cm–1 cannot be unambiguously attributed to quartz or 1150–900 cm–1 region due to no absorption saturation at the ATR pe-
hydrosilicate, although some discussion exists in the literature [60]. netration depth, while FTIR-PAS measurements of the soil in this region
Still these peaks reside on a shoulder of intense peaks at 1170 and experience a serious change in relative peak heights for 1170, 1130,
1153 cm–1 corresponding to main absorption bands of quartz (Figs. 4 and 950 cm–1 due to the saturation effects as discussed in the previous
and 7), so that the assessment of these minor components using peaks at section. However, the lower radiation intensity and shallower optical
1200 and 1190 cm–1 is hardly possible. penetration depth in ATR does not provide enough absorption to reveal
The region of 1190–900 cm–1 is not well-defined intensity-wise, as the overtone and combination bands of matrix minerals (Fig. 4) and
the intensities are distorted due to saturation effects [46,48]. As the they can be revealed only for a long accumulation time with low signal-
absorption coefficient of crystalline components of the soil matrix is to-noise ratios (Fig. 8). To the contrary, these overtone vibrations are
about 4000–10,000 cm–1 at wavenumbers of 900–1100 cm–1 [69], the induced in FTIR-PAS even for high rapid-scan frequencies (and, thus,
signal generation shifts from a thermally governed (Fig. 1a) to a ra- shallow penetration depths), and crystalline matrix forms can be as-
diation-governed mode (Fig. 1b), and the peaks become distorted in- sessed in FTIR-PAS, even rather low-intensity combination modes at
tensity-wise [46]. Well defined overtone and combination bands are 2000 cm–1 can be found. It is noteworthy that other FTIR modalities
also the manifestation of this. The same picture is observed for quartz usually require a rather significant absorption to reveal overtone bands,
and large to medium soil fractions. The same spectra were observed for and in the case of minerals and optical quartz samples, a preparation of
rapid and slow-scan modes (Fig. 6) with significantly different pene- thin films of various thicknesses are required to reveal either main or
tration depths, which is also an evidence of radiation-based character of overtone regions by transmission modes [60,71]. Still, several samples
these saturation effects. In amorphous SiO2, the same saturation effect are required for the whole range of 6000–300 cm–1, while FTIR-PAS

7
P.K. Krivoshein, et al. Photoacoustics 18 (2020) 100162

Fig. 7. Photoacoustic spectra (Bruker Vertex 70, 1.6 kHz) of a

shelterbelt sample of Kursk chernozem, fraction 20–30 μm (red),
and quartz sand, fraction 10–50 μm (black). Photoacoustic mea-
surement parameters: resolution, 8 cm–1; 128 scans; preamplifier
gain, ×200 (position 7) for the reference and ×2000 (position 10)
for the sample. Spectra are smoothed, wavenumber-corrected,
background-corrected, and not normalized.

provide the full band spectra (apart from the saturated region) from a spectra according to internal-standard (guide) concept, when some part
single run. Thus, from the viewpoint of inorganic soil constituents, PAS of each sample is considered the same despite the sample differences.
more readily provides more detailed information, which under the Candidates for such an internal standard in soil spectra may be
same conditions is produced under transmission measurements in thin peaks of major inorganic components. Among three main components
films [60,71]. From the viewpoint of SOM, its contribution is detect- of chernozem soils, illite and smectite cannot be selected as they may
able, although the sensitivity is not high (see Section 3.3 below) and have a different composition in the soil matrix and thus show some
sample preparation techniques like SOM isolation or annealing should changes in the characteristic peaks. To the contrary, quartz and hy-
be used [57,58]. From this viewpoint, FTIR-PAS have the same ad- drosilicate band positions are much more stable [60,62,63] and char-
vantages and disadvantages as DRIFT, which is discussed in the lit- acteristic. Still, the region of 1150–900 cm–1 cannot be used in FTIR-
erature [66]. Also, it is noteworthy that ATR spectra of soil fractions in PAS due to the peak intensity distortion in this area due to saturation
the main mineral part at 1200–300 cm–1 are well resolved, and it seems and also should be avoided due to possible specular reflections, espe-
expedient to use PAS and ATR modalities together for a more detailed cially for large particles, similarly to previously discussed DRIFT
information on soil structure and composition, which was out of frames modalities [66]. The region below 900 cm–1 is much more promising as
of this study. it holds the major lattice peaks of SiO2 at 797, 695, 450, and 394 cm–1.
However, this region may overlap with SOM bands (Table 2) as well as
with a priori unknown bands of clay minerals and smectite/illite con-
3.2. Selection of internal standards for sample comparison stituents.
In the shortwave region, characteristic peaks of clay minerals at
Contrary to many existing studies on soil properties by FTIR-PAS, 3700–3600 cm–1 are narrow and used for calculating some soil indices
when data processing consisted in normalizing the amplitudes in the [72], see next section. However, they are overlapped with a OHe bands
whole studied range before applying partial least square (PLS) models, at 3600–2600 cm–1 that is difficult to compensate and also can change
so that the spectrum area integral was equal to one [31,35], we worked its intensity after annealing [67]. In the overtone region, as discussed in
with the spectra from initially different samples (size fractions or dif- the previous section, the peak at 1615 cm–1 cannot be used due to huge
ferent land uses, Sections 3.4 and 3.5 below). Thus, we normalized the

Fig. 8. ATR (black; 256 scans; resolution, 0.5 cm–1, smoothing by

17 points) and photoacoustic (red, 1.6 kHz) spectra of the quartz
overtone bands for a quartz sand sample (fraction 10–50 μm). ATR
spectrum is received for a long accumulation time for the com-
parison with FTIR-PAS spectrum and shows a high noise level.
Photoacoustic measurement parameters: resolution, 8 cm–1; 128
scans; preamplifier gain, ×200 (position 7) for the reference and
×2000 (position 10) for the sample; ATR measurement para-
meters: 256 scans, resolution 0.5 cm–1), FTIR-PAS spectrum is
upscaled to match the ATR spectrum and shifted upwards for the
readability sake. Instrument, Bruker Vertex 70.

8
P.K. Krivoshein, et al. Photoacoustics 18 (2020) 100162

overlap with the absorbed-water peak, also it is in the range of water methods. No other peaks involving aluminum- and magnesium-con-
vapors in both the reference and sample spectra and is close to the taining minerals show a chemical shift depending on the concentration
intense peak of black carbon (Fig. 3), which may distort the shape and of mineral components, so they probably cannot be used for assessment
intensity of this peak. of mineral components.
Thus, most promising as an internal standard is the triplet of SiO2 Also, we attempted to used FTIR-PAS spectra for assessing the
combination bands at 2050–1750 cm–1 (Fig. 4). The comparison of crystallinity of illite components by calculating so-called Flehmig index
samples of various types, fractions, and before and after the annealing (I750/ I3630 ) [72]. The results showed that for most fractions, its value is
procedure (Section 2.1.4) showed that the relative intensities and 0.2–0.3, which corresponds to a metamorphic illite. However, this
shapes of these peaks change insignificantly. From the viewpoint of calculation was hindered by the not very advantageous shape of the
SOM analysis, in several research papers, the region of 2000–1200 cm–1 band at 750 cm–1 (a rather weak shoulder that produced a high error of
was claimed to be used for SOC/SIC related soil analysis due to little measurements). Still, the application of a mineralogical index to soil
interference in the peaks of inorganic species and not an individual sample seems rather promising for the applications of FTIR-PAS for soil
peak can be used without spectral processing. analysis due to the possibilities to get many intense and reproducible
This triplet was checked for the possible distortion of these peaks peaks from a single sample run without sample preparation.
during the acquisition of the reference-divided spectrum because of
different contributions from water vapors in the reference (Fig. 3) and 3.4. Soil size fractions
sample spectra. It was found that these peaks have the same area for
replicate measurements of the same soil sample (subsequent measure- The quality of FTIR-PAS spectra does not significantly differ for
ments of portions of the sample, repeatability conditions) and mea- various size fractions (Fig. 5). All fractions, except the silt fraction of
surements of the same sample in different days (reproducibility con- 1 μm show the characteristic peaks of quartz and hydrosilicate, see
ditions). Also, the areas of these peaks are coincident for quartz and soil Section 3.1. As discussed above, the region 2050–1750 cm–1 does not
samples with the similar grain size (Fig. 7). change due to dominating SiO2 vibrations, so any of the peaks at 1980,
It should be noted that such selection of an internal standard should 1880, and 1780 cm–1 can be used as internal-standard bands. In the NIR
be accompanied with signal preprocessing like that mentioned by K. region, aluminosilicate peaks can be used, however with caution.
Michaelian [49]. As FTIR-PAS operates with sample-to-reference divi- Previously, FTIR-PAS measurements revealed an absorption region
sion spectra, and without a manual data phase correction (Section in the wavenumber range of 1500–1350 cm–1 in samples near the sur-
2.1.3), the resulting peak intensity may change considerably, which face (0–10 mm) of paddy soils that was claimed to be dominated by
makes the use of an internal standard incorrect. CeO (carbonate) and CHe bending vibrations (organic materials); and
these vibrations were assumed as representing soil inorganic carbon
3.3. Quantitative estimations of mineral indices and SOM, respectively [35]. The range 1450–1380 cm–1 was used as the
soil total organic/inorganic ratio using a PLS model [35] and also for
IR spectroscopy can provide the quantitative data from peak posi- assessing carbonate contents in carbonate soils [17]. However, as dis-
tions as corresponding vibrations depend on the participating atoms, cussed above, this is not true for silicate soils, as silicate and quartz
the structure of characteristic fragments, and the clusters. In the spectra matrix exhibit multiple intense peaks in this region.
obtained, each of characteristic regions can be used for this purpose. In The necessity for multivariate calibrations is mentioned and the
the lattice region, 1200–300 cm–1, the peak positions correspond to generalized and self-adaptive models for total and exchangeable P, N, K
quartz as a main component, and the shifts in the peak positions are and SOM were proposed [13,15,18,38–40]. The complex nature of soils
within the error of measurements for crystalline SiO2 and hydrosilicate both in inorganic and organic components requires a very large col-
minerals. The only exception is a weak peak at 830 cm–1, which is lection of calibration samples, and the same type of soil is highly de-
present in the FTIR-PAS spectra of all fractions including silt fractions. manded [18]. However, in our case, as most peaks were identified as
It is attributed to illite and smectite and its position is known to depend inorganic matter, special treatment should be used for estimating SOM.
on the ratio of smectite and illite [61]. We found that its position does We selected annealing at 525 °C (Section 2.1.4), a widespread approach
not change from sample to sample by more than ± 3 cm–1, and it cor- for removing SOM from soils [3]. The comparison of spectra showed
responds to the ratio of illite : smectite of 1 : 1 according to previous almost no changes in the matrix region, while OH and overtone regions
findings [61], which agrees with this ratio found by independent changed significantly (Fig. 9). To sum up, water peaks at 3600 and

Fig. 9. Photoacoustic spectra (Bruker Vertex 70, 2.5 kHz) of a

cropland sample of Kursk chernozem, fraction 80–90 μm: (a) be-
fore (black) and after annealing at 525 °C for 3 h (red).
Photoacoustic measurement parameters: resolution, 8 cm–1; 128
scans; preamplifier gain, ×200 (position 7) for the reference and
×2000 (position 10) for the sample. Spectra were smoothed,
normalized in the range 2080–1820 cm–1, and not background-
corrected.

9
P.K. Krivoshein, et al. Photoacoustics 18 (2020) 100162

1640 cm–1 decrease, and the latter changes the silicate peak at 3.5. Samples of different soil use
1600 cm–1. As expected, peaks of CH at 2900–2860 cm–1 disappear
completely, as do rather significant wide absorption bands at Soil use type defines the SOM content [75], and the structure affects
1550–1450 and 1300–1150 cm–1. Most changes are in 1550–1470 cm–1 the stabilization processes of the SOM in general [76–78]. Nowadays,
(the long-wave shoulder of 1640 cm–1 peak), which may be due to a loss much attention is paid to the degradation processes of soils under their
of both SOM and coordinated water. Another changing range is active use, as well as to the means to control or restore chernozem
1300–1200 cm–1, which can be attributed to COe stretching. Bands at structure and hydrophysical properties [79–81]. Thus, we tested soils of
2260 and 2140 in the annealed spectra become more pronounced the same type but with significantly different history and intensity of
proving that they are SiO2 overtone bands. These changes manifested use. These samples belong to a 55-year-long field experiment of the V.V.
themselves in all the fractions starting with 100–250 μm and below. In Alekhin Tsentralno-Chernozemny Nature Reserve [54]. They can be
the cases of the lowest unseparated fraction (below 20 μm) and silt sorted depending on the organic contents. The intact steppe is an ex-
fractions, quantitative comparison is not possible as the most con- ample of chernozem with undisturbed properties and probably max-
venient triplet of quartz is absent, which hinders the normalization. imum SOM content, while forest shelterbelt is the previously used soil
The whole set of used interferometer modulation frequencies of 10, with restoration with fresh organic matter entering from the forest.
7.5, 2.5, and 1.6 kHz and 250 and 150 Hz (slow-scan modes) showed Permanent fallow is the soil annually cultivated without sowing and
that all the studied samples experience a relative decrease in the in- preventing the weeds; hence, no fresh organic matter has entered the
tensities of peaks attributed to inorganic matrix components: soil, contrary to the shelterbelt. Finally, cropland is the soil under
3700–3600, OH area 3600–2800, overtone triplet 2100–1900, silicate constant agricultural use with depleting SOM without any restoration.
peaks at 1700–1500, and the whole matrix area 1150–300 cm–1. Thus, these samples may be a good basis for a comparison of soils with
Weaker overtone bands at 2230 and 1530 do not manifest themselves similar SOM and inorganic constituents.
starting with frequencies above 1.6 kHz. However, peaks attributed to The FTIR-PAS spectra of whole soil samples for steppe, shelterbelt,
SOM (2900 and 2860 cm–1) also become statistically insignificant in fallow, and cropland do not differ significantly in all the most in-
rapid-scan modes. In fact, no new statistically significant features that formative regions. Thus, the analysis of separate fractions seems ex-
can be attributed to SOM appear for low modulation frequencies. pedient, as soil fractions are different from the contribution of soil
However, for silt fractions, due to lower contents of crystalline quartz, fertility [82–85]. The obtained fraction spectra differ from each other
the matrix effects are smaller, and the number of matrix peaks is also (Supplementary information, Fig. S2). To compare the spectra, we
lower, so varying the modulation frequency does provide a change in normalized them to a band of SiO2 internal standards (Section 3.2) as
spectra. its content in various land use sample differ insignificantly, so changes
Penetration depths for the selected modes correspond to estimated in other components, both depending on the SOM, amorphous, and
thermal diffusion lengths of 30–40 μm for slow-scan modes, 10–30 μm meso-structural components may be revealed after such an intensity
for 1.6–2.5 kHz and 4–10 μm for 7.5–10 kHz. Thus, for most fractions, normalization. According to the band identification (Section 3.1),
the penetration depth is shallower but comparable with the fraction changes in inorganic components, possible contributions from SOM,
sizes. The silt fraction is a different situation as the signal grain size ca. and the selection of internal standards (Section 3.2), we selected the
1 μm is smaller than the thermal-diffusion length, so in this case we following subranges. Overtone SiO2 bands 2052–1924, 1924–1836, and
have the average signal from many grains. It manifests itself in the in 1832–1751 cm–1 were used as internal standards; ranges 845–720 and
the independence of the silt fraction spectra from the modulation fre- 717–670 cm–1 were selected as they may reflect changes mainly due to
quency. inorganic matrices; and bands at 3050–2800, 1712–1570, 1540–1515,
Apart from this, the interpretation of the results should consider the 1480–1440, 1420–1365, 1350–1315, and 1310–1225 cm–1 were se-
soil particle structure. In existing papers, the comparison of modulation lected as possibly containing SOM components and mostly quartz
frequencies is based on the model of layered soil particles [73]. How- contributions that may be corrected by normalizing with a SiO2 internal
ever, in our opinion, this model for soil particles is not very realistic as standard. As expected, for all three selected internal-standard bands, all
usually soil particles have a very thin layer of SOM with SOM ag- the ratios between integral intensities 2052–1924, 1924–1836, and
gregates attached to the surface of larger matrix particles [74]. This was 1832–1751 cm–1 do not change for all the studied soil types, size frac-
further proven by the comparison of samples of different soil use. tions, and modulation frequencies.
Comparing size fractions, it was found that coarse fractions

Fig. 10. Spectra of Kursk chernozem, fraction 2–5 mm(Bruker

Vertex 70, 10 kHz), with different type of land use: intact steppe
(light green), shelterbelt (dark green), permanent fallow (black),
and cropland (red). Photoacoustic measurement parameters: re-
solution, 8 cm–1; 128 scans; preamplifier gain, ×200 (position 7)
for the reference and ×5000 (position 11) for the samples. Spectra
are smoothed, wavenumber-corrected, and background-corrected
and normalized by the range of 1924–1836 cm–1.

10
P.K. Krivoshein, et al. Photoacoustics 18 (2020) 100162

Fig. 11. Integrated peak area ratios for bands 1710–1570 to

1924–1836 cm–1 for interferometer modulation frequencies
10.0, 7.5, 2.5, and 1.6 kHz and five size fractions of chernozem
soil land-use types. The details of spectra acquisition are given
in Fig. 10. Spectra are smoothed, wavenumber-corrected, and
background-corrected and normalized by the range of
1924–1836 cm–1.

experience more notable changes compared to fine fractions (see the differences compared to entire soils. FTIR photoacoustic modality
example in Fig. 10). Ratios for bands at 1540–1515, 1480–1440, shows a much higher sensitivity in the middle-wave range of the mid-IR
1420–1365, 1350–1315, 1311–1225 cm–1 to internal standards range (SiO2 overtone range) compared to an attenuated total reflection
(2052–1924, 1924–1836, or 1832–1751 cm–1) provide similar results modality and provides the information similar to a diffuse-reflectance
(Fig. 11). The maximum ratios were found for the modulation fre- modality but without sample dilution. FTIR photoacoustic measure-
quency of 10.0 kHz, and the ratio drops down in a similar matter with a ments are possible for soil aggregates up to 5 mm without sample de-
decrease in the modulation frequency. This can be accounted for a composition or milling, which a unique property of this modality.
larger contribution from surface groups at high modulation frequencies. In our opinion, it seems important that no characteristic peaks in
At this stage, we ran preliminary tests for a limited collection of sam- photoacoustic spectra of chernozem soils are free from overlapping of
ples, so it is difficult to attribute these changes to silicate, water, or soil matrix components, by default. Thus, for studied silicate-based
SOM groups, but most changes were observed in the ranges showing chernozem soils, despite a high level of soil organic matter, matrix
difference peaks in annealing experiments. minerals are dominant in the whole spectrum, and the organic-matter
For the band at 3050–2800 cm–1, the signals for all the fractions analysis is hardly possible without destructive sample preparation or
increase with a decrease in the modulation frequency. The baseline organic-matter extraction or on some not-so-obvious assumptions.
correction in this area does not change the situation, so this behavior Inorganic-component analysis appears to be a more promising area for
can be attributed to higher signals from SOM at this CHe region at nondestructive photoacoustic FTIR as it can be based on large mineral
lower modulation frequencies as the thermal penetration depth under databases and approaches to quantitative assessment based on mineral
interferometer-modulation frequencies of 1.6 and 2.5 kHz correspond bands of different origin.
to probing the whole soil particles of fine fractions and a significant part An important feature is that quartz overtone peaks at
of coarser fractions with more contribution from SOM. 2000–1700 cm–1 can be used as internal standards of soil samples of the
From the viewpoint of different land uses, the bands at 1540–1515, same type for a more balanced spectra comparison. A drawback of
1480–1440, 1420–1365, 1350–1315, and 1310–1225 cm–1 provide a photoacoustic FTIR of soil components is rather sophisticated data
similar picture (see Fig. 11 as an example): for coarse fractions shel- processing, which is a huge asset in basic research of selected samples,
terbelt samples provide the highest signal followed by intact steppe; or the necessity for some correlation or factor analysis
cropland usually shows lower signals, and permanent fallow shows [16,18,19,31,38,63]. However, they are rather inappropriate for serial
signals comparable or lower than the cropland samples. For finer or more or less rapid analysis of multiple samples (and which is not
fractions, the differences are smaller, but the division of samples into cured by PLS models due to possible bias introduced at the initial
steppe/shelterbelt and fallow/cropland pairs remain. The same picture spectrum acquisition). Thus, some modelling and strict but simple data-
is for ranges 845–720 and 717–670 cm–1, here both coarse and fine handling algorithms are required for gaining more reliable and re-
fractions are divided into unused and used land type pairs. For producible data in FTIR PAS. Still, the methodological approaches de-
3050–2800 cm–1 range, shelterbelt still has the maximum signal, but veloped in this study together with previous findings seem reliable
close to them is fallow. A detailed discussion of the changes in cher- enough for using in soil analysis including both meso- and micro-
nozem soil on the land use was beyond the frames of this paper, but the aggregate levels.
difference in land types is in agreement with the behavior of the same
soils in thermogravimetric experiments [53].
Financial support

4. Conclusions This work was supported by the Russian Science Foundation, grant
no. 19-13-00117.
Thus, extended mid-IR photoacoustic spectra of chernozem soils of
various agrogenesis conditions show differences depending of the land
use that can be used as a basis for advanced soil studies. It seems im- Transparency document
portant that apart from well-known features of depth analysis by FTIR
photoacoustic modalities, FTIR-PAS provides rather reproducible con- The Transparency document associated with this article can be
ditions for various size fractions, and these fractions hold more found in the online version.

11
P.K. Krivoshein, et al. Photoacoustics 18 (2020) 100162

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University (1999–2000), FZK (Germany, 2002), and UAMS
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Proskurnin lie in photonics and photothermal and photo-
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morphic chernozems in the forest-steppe zone (Belgorod oblast), Eurasian Soil Sci.

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