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Article

The Influence of Selected Herbicides on Soil Organic Matter: Determining the Sustainable Development of Agroecosystems

by
Lilla Mielnik
1,*,
Brajan Bernacki
1 and
Jerzy Weber
2
1
Department of Bioengineering, West Pomeranian University of Technology in Szczecin, Papieża Pawła VI 3, 71-459 Szczecin, Poland
2
Institute of Soil Science, Plant Nutrition and Environmental Protection, Wrocław University of Environmental and Life Sciences, Grunwaldzka 53, 50-375 Wrocław, Poland
*
Author to whom correspondence should be addressed.
Sustainability 2025, 17(4), 1376; https://doi.org/10.3390/su17041376
Submission received: 8 December 2024 / Revised: 16 January 2025 / Accepted: 6 February 2025 / Published: 8 February 2025
(This article belongs to the Section Soil Conservation and Sustainability)
Browse Figures
Versions Notes

Abstract

:
Soil organic matter (SOM) is a key component of soil that determines the possibility of sustainable development of the environment by influencing, among other things, the binding and migration of elements in the soil. The properties of SOM are largely dependent on the properties of humic acids (HAs). New information about changes in their structure, determining their characteristics, can be obtained on the basis of their optical properties. The aim of this study was to assess the influence of the selected herbicides on the optical properties of HAs indicating changes in their structure. HAs were extracted from the mollic horizon of different phaeozems. The effect of HA interaction with two herbicides was assessed using UV–Vis spectroscopy and fluorescence. The investigation indicated clear differences in the structure of the HA molecules investigated as a result of interaction with the herbicides used. Each herbicide showed a different effect, likely due to the adjuvants used, which enhanced or weakened the process of HA–herbicide–HA complex formation. The results obtained show that the different additives used in the commercial products strongly influence the ability of HA to bind pesticides.

1. Introduction

For centuries, the main driver for improving land cultivation techniques was the criterion of quantity, and the aim of agriculture was to produce as much food as possible. Currently, the approach to farming is changing, and the aim is to produce high-quality products. A marker of this new way of thinking about agriculture is the reduction in the use of a variety of active substances for agricultural crops, affecting the biochemical properties of the soil and disturbing the natural environmental balance [1,2]. One broad group of active agents is pesticides. In addition to their beneficial effects on yield, their negative effects on the environment are increasingly recognised.
Pesticides are a very diverse group of chemical substances used in agriculture to control weeds or to protect crops from pests. Taking into account the mode of action of pesticides, a distinction is made between zoocides, fungicides, and herbicides and substances such as plant growth regulators, attractants, and repellents. These are biologically active chemical substances of natural origin or produced by synthesis. They have the ability to disrupt the growth of unwanted organisms through biochemical reactions [3,4,5]. Pesticides are chemical compounds that are very abundant in the environment because they are commonly used and have a short degradation time. The use of pesticides has a number of benefits; however, their presence in the environment can cause threats to the biocenosis [5,6,7,8,9,10]. Particularly dangerous is their leaching from the soil and accumulation in the aquatic environment [8]. Impairment of soil ecosystem functions by herbicides can have long-lasting effects, posing a potential long-term threat to the environment and thus, to soil quality.
Crop protection products are complex substances. In addition to their active compounds, they include various additives such as solvents or carriers (e.g., water, xylene, kaolin). Adjuvants are additives that modify or activate the effectiveness of the crop protection product. The behaviour of pesticides in the soil is regulated by a number of processes, such as biological and chemical degradation, sorption–desorption, runoff and leaching, and uptake by plants. These processes determine the fate of pesticides, including their migration in the soil and their transfer to water, air, or food. The extent of these processes depends on their chemical nature and soil properties [4,11].
One of the crucial factors determining the fate and retention of agrochemicals applied to soil is the content of organic matter [12]. Soil organic matter (SOM) is the main adsorbent of non-ionic herbicides. It therefore determines the concentration of these herbicides in the soil solution and regulates their transport down the soil profile. Therefore, SOM is one of the main factors influencing soil agrochemical doses [13,14]. One of the frequently studied fractions of SOM are humic acids (HAs), which are formed by various complex biochemical processes and are a mixture of different organic compounds. They contain a large number of phenolic, quinone, hydroxyl, and other groups that are formed by complex physicochemical processes during the processing of plant, microbe, and animal remnants [15]. Hydrophobic groups present in HAs can interact with the hydrophobic structures of herbicides, thus affecting their transformation and migration in the environment [16]. Their most important functions comprise their high reactivity and ability to sorb [17]. HAs can interact with herbicides through covalent bond formation or sorption, which promotes herbicide degradation and reduces the herbicide risk in the environment. Their surface has many active functional groups (such as hydroxyls or carboxyls) that can contribute to strong pesticide binding [18,19].
There is a lack of studies in the literature providing an in-depth understanding of the transformation and migration of commercial products in the environment. Understanding the fate of these substances in the soil is fundamental to accurately assess their behaviour in the environment and is crucial to ensure the safe use of these products. Therefore, the aim of our study was to assess the influence of selected herbicides on the optical properties of HA, indicating changes in their structure. Two commercial products containing sulfonylureas herbicides, chlorosulfuron and tribenuron-methyl, were selected for the study. The selected products are widely used in crop protection due to their high efficacy against specific crop groups without interfering with the physiological processes of the crop. The study was conducted as a laboratory experiment by saturating HA with the above herbicides. The effect of the interaction of HA with the sorbed herbicides was evaluated using spectroscopic methods: UV–Vis and fluorescence analysis. The latter method allows the detection of subtle changes in the structure of organic substances that cannot be detected by commonly used methods, such as NMR.

2. Materials and Methods

To eliminate as much as possible the influence of soil properties on the obtained results, the soils studied were four phaeozems (labelled after city names M-Magnice, C-Ciepłowody, P-Pyrzyce, K-Ketrzyn) derived from diverse parent rocks under different climatic conditions in Poland (Figure 1). They are located in agricultural areas where various crops are grown. Due to the different agroecological conditions of the area from which they originated, they showed different basic physicochemical properties (Table 1).
Soil samples were taken from the mollic horizon at randomly selected locations and then mixed and combined in one sample. The collected soil was air dried; the plant debris was removed, ground, and passed through a 2 mm mesh sieve.

2.1. Humic Acid Extraction

HA extraction and purification was carried out according to a modified method proposed by the International Humic Substances Society [20]. In the first extraction step, soil samples were decalcified with 0.05 mol H2SO4 in a double rinse. The soil remaining after decalcification was flooded with a 0.1 mol NaOH solution (soil to solution ratio was 1:10) and shaken for 4 h on a rotary shaker. The alkaline suspension was left to settle overnight. The next day, the solution was centrifuged (4000 rpm for 20 min). The resulting filtrate was collected in separate dishes. The extraction was repeated three times. The collected humic substance (HS) extracts were acidified to pH 1.5–2.0 using 4 mol H2SO4, and the suspension was left overnight. The precipitated HA was centrifuged. The HA obtained was then purified from the mineral portion using HCl-HF solution (5 cm3 HCl + 5 cm3 HF + 990 cm3 distilled water). The purified HA was washed with distilled water until the chloride reaction disappeared. The resulting precipitate of pure HA was frozen and dried in a freeze-dryer.

2.2. Herbicides Characteristics

Two commercial formulations for foliar and soil application were chosen for the study: Pleban 75 WG and Glean 75 W. Their characteristics are shown in Table 2. The active ingredient present in both products is a sulfonylurea derivative at a concentration of 750 g/kg (75%). Both products belong to the same HRAC (Herbicide Resistance Action Committee, Monheim, Germany) category B, where the mechanism of weed control occurs by blocking the synthesis of amino acids from the ALS (acetolactate synthase) inhibiting group. The active substances of both herbicides, being extremely toxic to aquatic organisms, are assigned to group H410. They are rapidly broken down in the soil, which limits their uptake by the roots.

2.3. Saturation of Humic Acids with Herbicides

HA saturation with selected herbicides was carried according to the OECD (Organisation for Economic Co-Operation and Development, Paris, France) Guideline for the Testing of Chemicals no. 106 and the standard for testing MCD chemicals. The experimental conditions were chosen on the basis of the values of the Koc coefficients of the active substance and its absorption potential of the soil constituents. Saturation was carried out at a constant carbon concentration of the HA fraction. The saturation procedure consisted of calculating the appropriate amounts of HA, herbicide, and solvent (in the form of acetone) required for the preparation. Such a mixture was left for 24 h in a dark room under constant stirring, and then allowed to evaporate for 24 h until the sample was dried.

2.4. Preparation of Humic Acid Solutions for Spectroscopic Analyses

Based on the results of the elemental composition of the HA under study, solutions for analysis were prepared so that the carbon concentration in solution was 10 mg dm−3. Pure and saturated HA were dissolved in a solution of 0.1 M NaOH. To obtain homogeneous solutions, they were subjected to ultrasound for 15 min and then shaken on an orbital shaker for 24 h. The following day, each solution was pre-filtered through a 0.2 mm pore size blotting paper filter. Prior to testing, each sample was filtered through a syringe filter with a pore size of 0.45 μm.

2.5. UV–Vis and Fluorescence Analyses

Registration of the UV–Vis absorption spectra of the HA solutions was carried out using a Jasco 770 UV–VIS-NIR spectrometer (Hachioji-shi, Tokyo, Japan). A quartz cuvette with an optical path length of 1 cm was used for the study. Measurements were carried out at a constant temperature of 25 °C.
The fluorescence spectra were recorded using a Hitachi F 7000 spectrofluorometer (Chiyoda, Tokyo, Japan). Synchronous scan spectra were measured in the range of 220–620 nm, with the scan difference constant Δλ = λem − λex = 20 nm. The scan speed was 240 nm min−1.
Three-dimensional fluorescence spectra (EEM) were scanned at emission wavelengths from 250 to 600 nm by varying the excitation wavelengths from 200 to 550 nm. The monochromators of the excitation and emission slits were 5 nm and 10 nm, respectively, and the scan speed was 1200 nm min−1.

3. Results and Discussion

3.1. UV–Vis Spectra

The absorption spectra of the studied HAs are characterised by a monotonic course over the whole UV–Vis range (Figure 2). The differences lie mainly in the absorption intensity, which is particularly pronounced in the UV region, and in the slope of the spectra analysed. In the case of pure HA, the highest absorption intensity is shown by HA from clay soil (K sample). The trend of the changes in absorbance was as follows: K > P > M = C.
The addition of both preparations—Glean and Pleban—resulted in changes in absorbance intensity over the whole spectral range. The HA from the clay soil saturated with Pleban (K sample) showed the highest absorbance, while the absorbance of the other HA was lower and similar (K > M = C = P). In the visible range, the addition of both preparations reduced the absorbance values of all the HAs tested.
A characteristic feature of the spectra of uncontaminated HA is the appearance of a maximum wavelength in the 280–285 nm wavelength range, which is characteristic of humic acids from different environments [21,22,23]. This maximum is characteristic of phenolic and quinone structures, benzoic acid derivatives, and/or polycyclic aromatic hydrocarbons, and the absorbance in this region increases with the degree of condensation of the aromatic rings [24,25,26].
The addition of both preparations caused changes in the position of the absorption maxima in the short wavelength spectral region, as well as a change in the slope. The spectra of contaminated HAs are steeper compared to those of pure HAs. In addition, there was a hypochromic shift of the characteristic absorption maximum to 260 nm after saturation with Pleban (Figure 2b). In contrast, saturation with Glean caused an additional maximum to appear at 235 nm (Figure 2a). This is due to the effect of different functional groups on the binding of both herbicides to HA. The formation of a donor–acceptor complex allows for electron exchange and thus favours the modification of the absorption spectra in the UV region by adsorbed organic pollutant molecules.
Based on the absorption spectra obtained, the values of selected parameters were counted (Table 3), providing information on the structure, degree of aromaticity and aliphaticity, molecular weight, and maturity of the organic molecules [27]. The effect of the interaction of the herbicides with HA, which alters their absorption capacities, is marked in the values of the ratios E235:E280, E260:E365, and E260:E436. The UV absorption efficiencies are mainly related to the substituent groups of the chromophores in the aromatic benzene ring or in the aliphatic chains. Variations in the values of these ratios suggest a preferential modification of the aromatic chromophores, depending on the chemical composition of the commercial products used. The interaction of HA with herbicides can lead to the degradation of many functional groups to simple aromatic carboxylic acid products [28], which may also favour the destruction of charge transfer complexes [29]. The low values of E465:E665 and ΔlogK are characteristic of well-formed, highly “mature” HA [30,31,32] and indicate a relatively high molecular weight and the presence of condensed aromatic structures. The addition of the applied herbicides did not significantly affect the changes in the values of these coefficients.

3.2. Synchronous Scan Fluorescence (SSF) Spectra

Uncontaminated HA shows three main fluorescence emission regions: the 240–290, 300–340, and 360–580 nm wavelength ranges (Figure 3).
Saturation with both herbicides caused changes in energy transfer, resulting in a decrease in fluorescence in the long-wavelength area of the spectrum (above 340 nm) and an increase in fluorescence observed in the 240–340 nm wavelength region, especially after Pleban saturation (Figure 3b). This suggests the appearance of structural moieties (methoxy and nitrated groups) rich in electron-donating substituents [33]. The formation of a donor–acceptor complex allows for electron exchange and thus favours the modification of the fluorescence spectra by the adsorbed organic impurity molecules.

3.3. Three-Dimensional Fluorescence (EEM) Spectra

HAs consist of macromolecules with different functional groups, so their fluorescence characteristics are very complicated. Figure 4 shows the contour 3D fluorescence spectra for HA before and after saturation with Glean and Pleban. The EEM spectra of the four uncontaminated HAs are characterised by the presence of an intense, broad maximum δ in the λex/λem 270–280/450–500 wavelength region and two weak peaks, γ and ω, in the long-wavelength part of the spectrum. The position and fluorescence intensity of the identified peaks are shown in Table 4.
The C samples showed the highest fluorescence values for the identified fluorophores, while the K samples showed the lowest values (Table 4). In contrast, the EEM spectra of HA from soil A saturated with Glean and Pleban showed a completely different picture compared to that for the unsaturated samples. The EEM spectra of HA from soil C saturated with Glean (C-GL) are characterised by the occurrence of the same peak δ, with similar fluorescence intensity and the appearance of two unique peaks, α and β, in the short-wavelength part of the spectrum (Table 4). In contrast, the α and β peaks are very broad and exhibit very high efficiency due to the interaction with Pleban. In both cases, the γ and ω peaks are weakened or completely quenched, indicating that the fluorophores responsible for the fluorescence in the long-wavelength region are blocked, e.g., by the formation of a non-luminescent complex connected with the interaction between the quencher and the fluorophore.
The changes in the EEM spectra induced by the reaction of HA with the herbicides tested are closely related to the reactivity of the HA itself towards the herbicide and the molecular structure of both the HA and the herbicide molecules and especially, to the presence of the functional groups. For commercial products, enhancers of the active ingredient also play an important role. One possible mechanism causing an increase in fluorescence after the application of Pleban could be the aggregation of the complex [5]. On the other hand, the strong increase in fluorescence may be related to the degradation of many functional groups to simple aromatic carboxylic products [28].
Many studies on the interaction of HA with pesticides have shown fluorescence quenching [34,35], while our studies showed that the addition of herbicides from the ALS inhibitor group caused a significant increase in fluorescence intensity in the short-wavelength region and only a slight decrease in the long-wavelength region.

4. Conclusions

The results provide useful information for predicting the interaction of HA with herbicides. Our study indicated a significant effect of selected commercial products on the molecular structure of HA. In addition to the effect of the type of active ingredient itself, the excipients added to the commercial formulation also appear to play an important role. Analysis of the spectroscopic properties showed that the interaction of HA with the tested herbicides did not significantly affect their relatively high molecular weight and condensed aromatic structures. On the other hand, it can cause the formation of a donor–acceptor complex and the appearance of structural moieties (methoxy and nitrated groups) rich in electron-donating substituents.
The composition of commercial products significantly alters the strength and ability of organic matter to bind chlorosulfuron and tribenuron-methyl. The additives used are more competitive in forming bonds with HA active sites and thus enhance, weaken, or mediate the formation of herbicide–HA complexes. Analysis of the spectroscopic properties showed that the interaction of HA with the tested herbicides did not significantly affect the size and molecular weight of the studied HAs or the content of condensed aromatic structures. This provided additional information regarding changes in their properties, but their interpretation is difficult at this stage of knowledge. For this reason, it seems advisable to carry out further studies on these phenomena using advanced analytical techniques such as Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), X-ray absorption near edge structure (XANES) spectroscopy, and pyrolysis field ionization mass spectrometry (Py-FIMS).

Author Contributions

Conceptualization: L.M.; methodology: L.M. and B.B.; formal analysis: L.M. and B.B.; investigation: L.M. and B.B.; writing—original draft preparation: L.M.; writing—review and editing, L.M. and J.W.; visualization: L.M. and J.W. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Data are available on request from the authors.

Conflicts of Interest

The authors declare no conflicts of interest.

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Figure 1. Location of the investigated soils: M-Magnice, C-Ciepłowody, P-Pyrzyce, K-Kętrzyn.
Figure 1. Location of the investigated soils: M-Magnice, C-Ciepłowody, P-Pyrzyce, K-Kętrzyn.
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Figure 2. UV–Vis spectra of the pure HA (M, C, P, K) and (a) HA saturated with Glean (M-GL, C-GL, P-GL, K-GL) and (b) HA saturated with Pleban (M-PL, C-PL, P-PL, K-PL).
Figure 2. UV–Vis spectra of the pure HA (M, C, P, K) and (a) HA saturated with Glean (M-GL, C-GL, P-GL, K-GL) and (b) HA saturated with Pleban (M-PL, C-PL, P-PL, K-PL).
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Figure 3. SSF spectra of the analysed pure HA (M, C, P, K), (a) HA saturated with Glean (M-GL, C-GL, P-GL, K-GL), and (b) HA saturated with Pleban (M-PL, C-PL, P-PL, K-PL).
Figure 3. SSF spectra of the analysed pure HA (M, C, P, K), (a) HA saturated with Glean (M-GL, C-GL, P-GL, K-GL), and (b) HA saturated with Pleban (M-PL, C-PL, P-PL, K-PL).
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Figure 4. EEM spectra of the analysed unsaturated HA (M, C, P, K), HA saturated with Glean (M-GL, C-GL, P-GL, K-GL), and HA saturated with Pleban (M-PL—n.i., C-PL, P-PL, K-PL).
Figure 4. EEM spectra of the analysed unsaturated HA (M, C, P, K), HA saturated with Glean (M-GL, C-GL, P-GL, K-GL), and HA saturated with Pleban (M-PL—n.i., C-PL, P-PL, K-PL).
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Table 1. Selected physicochemical properties of the soils from which the HA was extracted.
Table 1. Selected physicochemical properties of the soils from which the HA was extracted.
SoilpHKCICaCO3TOCTNTOC/TNSandSiltClayWRB
Textural Class
g kg−1%
M7.521.5321.21.0613.2294922loam
C7.391.0326.12.0312.8245719silt loam
P7.481.5424.62.1211.6393724loam
K6.660.6137.72.8013.4242947clay
Table 2. Physical and chemical properties of chlorosulfuron and tribenuron.
Table 2. Physical and chemical properties of chlorosulfuron and tribenuron.
HerbicideGlean 75 WGPleban 75 WG
Active substancechlorosulfurontribenuron-methyl
Chemical formulaC12H12ClN5O4SC15H17N5O6S
IUPAC name2-chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)carbamoyl]benzene-1-sulfonamideMethyl 2-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-methylcarbamoyl]sulfamoyl]benzoate
Structure diagramSustainability 17 01376 i001Sustainability 17 01376 i002
Solubility in water12,500 mg/L (20 °C)2483 mg/L (20 °C)
Molecular mass (g/mol)357.78395.39
AppearanceWhite crystalline solidWhite to off-white solid
logP−0.990.38
Acidity (pKa)3.404.65
Table 3. Selected UV–Vis absorbance coefficients.
Table 3. Selected UV–Vis absorbance coefficients.
SampleE235:E280E260:E365E260:E465E280:E665E465:E665ΔlogK
M1.342.365.1616.83.580.58
M-GL3.023.747.8219.53.570.59
M-PL2.274.509.2718.63.390.56
C1.332.334.9515.53.470.56
C-GL3.013.987.8818.63.550.58
C-PL2.184.118.6819.33.500.57
P1.282.204.3912.93.220.52
P-GL2.273.095.8714.43.270.54
P-PL2.385.0510.0817.63.250.54
K1.272.284.6513.83.310.53
K-GL2.983.957.3415.93.320.54
K-PL2.415.1110.2418.73.360.54
Pure HA (M, C, P, K); HA saturated with Glean (M-GL, C-GL, P-GL, K-GL); and HA saturated with Pleban (M-PL, C-PL, P-PL, K-PL).
Table 4. Position and fluorescence intensity of the identified maxima. Excitation–emission wavelength pairs (λex/λem) and corresponding fluorescence intensities (IFI) of the main fluorophores (α, β, δ, γ, and ω) of pure HA and HA saturated with Glean and Pleban.
Table 4. Position and fluorescence intensity of the identified maxima. Excitation–emission wavelength pairs (λex/λem) and corresponding fluorescence intensities (IFI) of the main fluorophores (α, β, δ, γ, and ω) of pure HA and HA saturated with Glean and Pleban.
αβδγω
λex/λemIFlλex/λemIFlλex/λemIFlλex/λemIFlλex/λemIFl
M----275/45541.3360/46223.3440/51513.1
M-GL230/34639.6285/34420.7277/44938.0365/46916.0450/5306.5
M-PLn.i.n.i.n.i.n.i.n.o.n.o.n.o.n.o.n.o.n.o.
C----274/46430.7359/47317.5442/52110.0
C-GL230/34640.7283/34443.8274/45229.0368/48014.2455/5257.5
C-PL233/352966286/352545------
P----276/46432.6365/46719.4441/51612.92
P-GL229/34734.5283/34626.8277/45634.0361/45816.5442/5208.8
P-PL232/3511287287/352672------
K----278/50115.7373/49116.4451/52611.9
K-GL225/34615.8287/34536.2285/44923.5361/47113.6440/5189.5
K-PL234/354465.6290/354665.0------
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Mielnik, L.; Bernacki, B.; Weber, J. The Influence of Selected Herbicides on Soil Organic Matter: Determining the Sustainable Development of Agroecosystems. Sustainability 2025, 17, 1376. https://doi.org/10.3390/su17041376

AMA Style

Mielnik L, Bernacki B, Weber J. The Influence of Selected Herbicides on Soil Organic Matter: Determining the Sustainable Development of Agroecosystems. Sustainability. 2025; 17(4):1376. https://doi.org/10.3390/su17041376

Chicago/Turabian Style

Mielnik, Lilla, Brajan Bernacki, and Jerzy Weber. 2025. "The Influence of Selected Herbicides on Soil Organic Matter: Determining the Sustainable Development of Agroecosystems" Sustainability 17, no. 4: 1376. https://doi.org/10.3390/su17041376

APA Style

Mielnik, L., Bernacki, B., & Weber, J. (2025). The Influence of Selected Herbicides on Soil Organic Matter: Determining the Sustainable Development of Agroecosystems. Sustainability, 17(4), 1376. https://doi.org/10.3390/su17041376

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