Soil Organic Matter Components Research Articles

Improved Characterization of Soil Organic Matter by Integrating FT-ICR MS, Liquid Chromatography Tandem Mass Spectrometry, and Molecular Networking: A Case Study of Root Litter Decay under Drought Conditions.

Understanding of how soil organic matter (SOM) chemistry is altered in a changing climate has advanced considerably; however, most SOM components remain unidentified, impeding the ability to characterize a major fraction of organic matter and predict what types of molecules, and from which sources, will persist in soil. We present a novel approach to better characterize SOM extracts by integrating information from three types of analyses, and we deploy this method to characterize decaying root-detritus soil microcosms subjected to either drought or normal conditions. To observe broad differences in composition, we employed direct infusion Fourier-transform ion cyclotron resonance mass spectrometry (DI-FT-ICR MS). We complemented this with liquid chromatography tandem mass spectrometry (LC-MS/MS) to identify components by library matching. Since libraries contain only a small fraction of SOM components, we also used fragment spectral cosine similarity scores to relate unknowns and library matches through molecular networks. This integrated approach allowed us to corroborate DI-FT-ICR MS molecular formulas using library matches, which included fungal metabolites and related polyphenolic compounds. We also inferred structures of unknowns from molecular networks and improved LC-MS/MS annotation rates from ∼5 to 35% by considering DI-FT-ICR MS molecular formula assignments. Under drought conditions, we found greater relative amounts of lignin-like vs condensed aromatic polyphenol formulas and lower average nominal oxidation state of carbon, suggesting reduced decomposition of SOM and/or microbes under stress. Our integrated approach provides a framework for enhanced annotation of SOM components that is more comprehensive than performing individual data analyses in parallel.

Changes in the Composition of Soil Organic Matter after the Transformation of Natural Beech Stands into Spruce Monoculture

The composition of soil organic matter is considered to have a key influence on C sequestration and global climate change and can be associated with changes in vegetation cover in the terrestrial ecosystem. Our study aimed to evaluate the soil chemical structures and various organic components from available or reactive to more stable forms in forest soils affected by acidification and after conversion from fairly close to natural beech (Fagus sylvatica) stands to a spruce (Picea abies) monoculture. Our results revealed that the beech stands had higher contents of dissolved organic carbon and low molecular mass organic acid compared to the spruce stands. The aliphatic CH groups within the soluble alkaline-extractable organic substance (AEOS) gradually disappeared with deeper soil horizons under both forest species, while the presence of aliphatic CH groups in the low-solubility AEOS was more pronounced in the A horizon under spruce and relatively increased with depth under beech stands. The carboxylic groups were more prevalent in deeper soil horizons, while polysaccharide chains and nitrogen functional groups decreased with depth under both forest stands but were more prevalent under beech than under spruce stands. These findings suggest that the stability of organic matter through the forest soil profiles increased due to the transformation of various organic compounds from litter to more stable organic matter with higher amounts of lignin components to greater amounts of carboxylic groups and aromatic groups in deeper soil horizons. Furthermore, a higher number of mobile components of soil organic matter and carboxylic acids, together with lower pH and cation exchange capacity under spruce, resulted in the leaching of nutrients, releasing risk elements into the soil solution and accelerating the podzolization process.

Soil organic matter components and sesquioxides integrally regulate aggregate stability and size distribution under erosion and deposition conditions in southern China

Water erosion considerably affects the stability and particle size distribution of soil aggregates, but the underlying mechanisms of water erosion remain unclear. To this end, we selected four landscape positions (top-, up-, mid-, and toe-slope) with distinct erosion and deposition characteristics on a typical eroded slope in southern China to conduct experiments- aiming to investigate the main drivers of soil aggregate stability during erosion and deposition processes. Soil samples were collected from 12 sites, and 4 size classes (>2, 2–0.25, 0.25–0.053, and <0.053 mm) of soil aggregates were obtained using the wet sieving method. The composition and stability of the soil aggregates, as well as the contents of organic (organic matter components) and inorganic (iron-aluminum oxides) cementing materials of different particle sizes, were determined. The results indicated that erosion significantly reduced the aggregate stability and the >0.25 mm water-stable aggregate content (WR0.25) (P < 0.05). The mean weight diameter (MWD) and geometric mean diameter (GMD) values of the soil aggregates at the eroding site decreased, and the fractal dimension (FD) increased. Furthermore, erosion markedly reduced the humic acid (HA) and fulvic acid (FA) contents in the bulk soils and soil aggregates, while the HA content showed no obvious difference between the eroding and depositional sites. In addition to the presence of complexed iron/alumina oxides (Fep/Alp), erosion markedly reduced the contents of amorphous (Feo/Alo) and free-form (Fed/Ald) iron/alumina oxides in the bulk soils and size fractions. Moreover, Fed/Ald, Fep and Feo/Alo were present in the microaggregates, while Alp was found in the macroaggregates. Additionally, boosted regression tree (BRT) analysis indicated that FA (36.70 %), Feo (19.00 %), and Ald (12.71 %) were the crucial predictors of soil aggregate stability. These findings further confirm that the organic and inorganic cementing materials in red soils collectively contribute to aggregate stabilization under the impact of erosion. This study facilitates a deeper understanding of the mechanisms governing soil aggregate stability in eroded landscapes, and provides a theoretical basis for biogeochemical cycling processes.

Soil organic matter components and characteristics of forest soil in spruce and sycamore plantations in the temperate region

The stability of soil organic matter (SOM) that governs soil organic carbon (SOC) storage depends on its characteristics and components, but little is known about how tree species in forest ecosystems affect SOM components and characteristics. In this study, we used FTIR spectroscopy to investigate plantations of two ecologically and economically significant tree species—namely, spruce (Picea spp.) and sycamore (Acer pseudoplatanus)—in order to determine how the different litter inputs and root-microbe interactions of these two plantations affect the functional groups, components, and characteristics of their SOM. Soil samples were taken from the topsoil (0–10 cm) and subsoil (10–20 cm). In the 0–10 cm soil depth, the SOM's hydrophilic, hydrophobic, and aromatic components differ between the spruce and sycamore plantations. The hydrophobic components constitute the primary constituents of the SOM of the two forest plantations, in contrast to the expected predominance of the hydrophilic component of the SOM. Also, the high hydrophobicity (hydrophilic/hydrophobic) in the subsoil of the spruce plantations was attributed to a decrease in hydrophilic components and a subsequent increase in hydrophobic components of the SOM. The sycamore plantations exhibited a higher SOM aromaticity and a greater degree of decomposition than the spruce plantations. The aforementioned distinctions emphasise the contrasting mechanisms involved in transforming and turnover of the two-tree species' soil organic matter (SOM).

The Use of Spectroscopic Methods to Study Organic Matter in Virgin and Arable Soils: A Scoping Review

The use of modern spectroscopic methods of analysis, which provide extensive information on the chemical nature of substances, significantly expands our understanding of the molecular composition and properties of soil organic matter (SOM) and its transformation and stabilization processes in various ecosystems and geochemical conditions. The aim of this review is to identify and analyze studies related to the application of nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopy techniques to study the molecular composition and transformation of organic matter in virgin and arable soils. This article is mainly based on three research questions: (1) Which NMR spectroscopy techniques are used to study SOM, and what are their disadvantages and advantages? (2) How is the NMR spectroscopy technique used to study the molecular structure of different pools of SOM? (3) How is ESR spectroscopy used in SOM chemistry, and what are its advantages and limitations? Relevant studies published between 1996 and 2024 were searched in four databases: eLIBRARY, MDPI, ScienceDirect and Springer. We excluded non-English-language articles, review articles, non-peer-reviewed articles and other non-article publications, as well as publications that were not available according to the search protocols. Exclusion criteria for articles were studies that used NMR and EPR techniques to study non-SOM and where these techniques were not the primary methods. Our scoping review found that both solid-state and solution-state NMR spectroscopy are commonly used to study the structure of soil organic matter (SOM). Solution-phase NMR is particularly useful for studying soluble SOM components of a low molecular weight, whereas solid-phase NMR offers advantages such as higher 13C atom concentration for stronger signals and faster analysis time. However, solution-phase NMR has limitations including sample insolubility, potential signal aggregation and reduced sensitivity and resolution. Solid-state NMR is better at detecting non-protonated carbon atoms and identifying heterogeneous regions within structures. EPR spectroscopy, on the other hand, offers significant advantages in experimental biochemistry due to its high sensitivity and ability to provide detailed information about substances containing free radicals (FRs), aiding in the assessment of their reactivity and transformations. Understanding the FR structure in biopolymers can help to study the formation and transformation of SOM. The integration of two- and three-dimensional NMR spectroscopy with other analytical methods, such as chromatography, mass spectrometry, etc., provides a more comprehensive approach to deciphering the complex composition of SOM than one-dimensional techniques alone.

Addition of Biochar and Fertiliser Drives Changes in Soil Organic Matter and Humic Substance Content in Haplic Luvisol

Humic substances (HSs) constitute a primary component of soil organic matter (SOM) and play a crucial role in soil formation and fertility. However, comprehensive information regarding quantitative and qualitative changes in HS following biochar’s application to soil still needs to be improved. This study reports on the impact of biochar application at rates of 0, 10, and 20 t ha⁻1 (B0, B10, B20), both with and without nitrogen fertilisation at varying levels (N0, N1, N2), on SOM and HS contents throughout the cropping seasons between 2014 and 2019. The findings reveal changes in SOM and HS contents due to biochar addition and fertilisation. Notably, the most substantial increase in soil organic carbon content was observed in the B20N1 and B10N1 treatments, in stark contrast with the reference B0N0 treatment. A decrease in humification of SOM was noted across all treatments involving biochar, whether alone or combined with different N fertilisation levels. An interesting positive change in HS contents was observed in B10N2, where an increase in humic acids and a decrease in fulvic acids enhanced HS stability and improved HS quality. These findings shed light on the intricate dynamics of SOM and HSs in response to biochar application and nitrogen fertilisation over multiple vegetation seasons of crops on loamy Haplic Luvisols in Central Europe.

Variations in the quantity and chemical composition of soil dissolved organic matter along a chronosequence of wolfberry plantations in an arid area of Northwest China

Abstract Background Dissolved organic matter (DOM) is the most active component of soil organic matter (SOM), playing a major role in regulating soil fertility and carbon cycling. However, the effects of different wolfberry (Lycium barbarum L.) planting ages on the chemical diversity of DOM and its interaction with soil physicochemical properties have not been comprehensively studied. In this context, we collected soil samples (0–10 cm) from wolfberry orchards at different planting ages (1, 4, 6, 10, and 13 years) and from a corn field (0 years) in the arid region of Northwest Ningxia in China to assess the changes in soil DOM quantity and quality using ultraviolet–visible absorbance, fluorescence spectroscopy, and parallel factor analysis. Results We found that the ages of the wolfberry plantation changed the contents of soil nutrients and SOM. In addition, significantly higher DOM concentrations were observed at wolfberry planting ages of 10 and 13 years than those in the control group (0 years) by 176.6 and 190.2%, respectively. The specific ultraviolet absorbance at 254 nm (SUVA254) and 254 nm to 365 nm ultraviolet absorbance ratio (E2/E3) values were decreased and increased, respectively, after wolfberry planting, indicating low aromatic and molecular weight compounds of soil DOM. The biogenic index (BIX) and fluorescence index (FI) of soil DOM ranged from 0.6 to 0.7 and 1.42 to 1.93, respectively, suggesting a combination of allochthonous and autochthonous sources. The short- and long-term wolfberry cultivations of 1 and 4 years decreased and increased the humification degrees of soil DOM, respectively. The contribution rate of the protein-like (C1) fluorescence intensity decreased, while that of the fulvic acid-like component (C3) increased with increasing wolfberry planting age, suggesting a change in the structure of soil DOM from protein-like to fulvic acids. In this study, total nitrogen (TN) and exchangeable Ca2+ were the main factors affecting the quantity and quality of soil DOM in the wolfberry orchards with different planting ages. Conclusions This study demonstrated that long-term wolfberry plantation enhances the accumulation of soil DOM and more complex compounds, thereby promoting soil organic carbon sequestration under different planting ages and land-use types in terrestrial ecosystems. Graphical Abstract

Humic and Fulvic Acids Promote Growth and Flowering in Petunias at Low and Optimal Fertility

Humic substances are components of soil organic matter that influence soil structure and fertility. Humic and fulvic acids can be extracted from soil and other organic sources, and are used as biostimulants to promote plant growth and increase nutrient availability and uptake. The goal of this study was to determine whether selected humic and fulvic acid–based commercial products would promote growth and flowering of petunia (Petunia ×hybrida) ‘Picobella Blue’ grown in soilless media with low or optimal fertilizer rates. Plants were grown in 11.4-cm pots filled with peat-based media [80:20 peat:perlite (v/v); pH 5.4]. Three biostimulant products were evaluated at different rates and application frequencies: Huma Pro, a liquid humic acid biostimulant; Fulvi Pro, a liquid fulvic acid biostimulant; and Micromate, a powder containing both humic and fulvic acids. In Expt. 1, Huma Pro and Fulvi Pro were drenched weekly onto the growing media at a rate of 5, 10, or 20 mL⋅L–1; Micromate was drenched weekly at a rate of 5, 10, 20, or 40 g⋅L–1. Plants were fertilized with either 50 mg⋅L–1 nitrogen (N) (low fertility) or 100 mg⋅L–1 N (optimal fertility) from Jack’s Professional 20N–1.3P–15.7K Petunia FeED each irrigation. Control plants received fertilizer but no biostimulant treatments. In Expt. 2, biostimulant treatments were drenched once at transplant, biweekly, or weekly at a rate of 1.25, 2.5, 5, or 10 mL⋅L–1 for Huma Pro and Fulvi Pro; and at 5, 10, 20, or 40 g⋅L–1 for Micromate. All plants received constant liquid feed at the lower fertilizer rate of 50 mg⋅L–1 N. In Expt. 1, plants fertilized with 100 mg⋅L–1 N and treated with 20 g⋅L–1 Micromate had the best performance. The average shoot dry weight was 32% greater than that of the control plants. Micromate (20 g⋅L–1)-treated plants had an average of five more flowers per plant, and they flowered 4 days earlier than untreated control plants. In Expt. 2, plants treated with 40 g⋅L–1 of Micromate weekly had the greatest shoot dry weight compared with the other treatments. Weekly Micromate treatments (40 g⋅L–1) resulted in plants with an average of 13 more flowers per plant, which flowered 7 days earlier than control plants. Plants treated with Fulvi Pro and Huma Pro at 20 mL⋅L–1 had a significantly greater concentration of potassium in shoot tissue, whereas Micromate treatments at 20 and 40 g⋅L–1 resulted in a greater concentration of phosphorous in the shoots. The humic and fulvic acids in Micromate improved petunia crop quality by promoting vegetative growth, increasing flower numbers, and reducing the time to flower.

Functional organic matter components in mangrove soils revealed by density fractionation

ABSTRACT The mechanisms underlying stabilization of soil organic matter (SOM) in vegetated coastal ecosystems, including mangrove forests, are poorly understood, limiting our ability to predict the consequences of disturbances. Here, we introduce density fractionation to mangrove soils to identify the distribution and properties of the functional components of SOM regarding degradation state, stability, and origin, namely, the free low-density fraction (f-LF), mineral-associated LF (m-LF), and high-density fraction (HF). Three soil cores (1 m) were collected in a mangrove forest on Ishigaki Island, Japan, and cut into 10 cm intervals and analyzed. Although HF was the most abundant, the massive production of mangrove fine roots resulted in a high abundance of LFs throughout the cores, which markedly differed from terrestrial soils. Relative abundance of LFs together accounted for 38–66% of total soil C. The m-LF was as abundant as f-LF and 1.6 times higher in relative abundance than the global average of terrestrial soils. The C/N ratios and δ13C values clearly increased with depth in all fractions, which was attributed to the increased contribution from roots. We found a consistent pattern in Δ14C values of density fractions. HF was the oldest with Δ14C between −149‰ and −97‰ followed by m-LF (between −130‰ and −87‰) and then f-LF (between −89‰ and 78‰), suggesting that mineral association may be pivotal in long-term carbon storage in the mangrove mineral soil. Our analysis successfully identified meaningful functional components of mangrove SOM, yet several questions remained unanswered, including a large variability in Δ14C in different cores. Future studies would benefit from a coupled analysis of the quantity and quality of density fractions and geochemical factors in mangrove soils.

Effect of High-volume Straw Returning and Applying Bacillus on Bacterial Community and Fertility of Desertification Soil

This study was conducted to explore the fertilization potential of the high-volume straw returning mode in cooperation with Bacillus and other functional flora on desertification soil and to analyze the changing characteristics of soil carbon, nitrogen, and phosphorus components and functional activities of flora, so as to provide a basis for efficiently improving desertification soil fertility. A randomized block experiment was conducted, setting straw not returning to field (CK) and high-volume straw returning of 6.00 kg·m-2 (ST1), 12.00 kg·m-2 (ST2), 24.00 kg·m-2+(ST3), 6.00 kg·m-2+Bacillus (SM1), 12.00 kg·m-2+Bacillus (SM2), and 24.00 kg·m-2+Bacillus (SM3). In this study, we conducted a randomized block experiment to investigate the effect of the treatment for soil microbial and nutrient contents using 16S rRNA high-throughput sequencing and soil biochemical properties analysis. Our results showed that:① the α diversity of the soil bacterial community was significantly reduced by the combination of high-volume straw returning and Bacillus application. ② The single mode of high-volume straw returning significantly enriched Proteobacteria and decreased the relative abundance of Actinobacteriota, and the effect of the combined application of Bacillus on the variability of bacterial community structure was more significant. At the genus level, the relative abundance of beneficial bacteria such as Pseudomonas, Rhodanobacter, and Bacillus increased significantly. ③ The functional prediction based on FAPROTAX found that the high-volume straw returning combined with Bacillus could significantly improve the decomposition potential of soil flora to organic substances and the transformation potential of nitrogen components. ④ Compared with that in the control, the application of Bacillus with high-volume straw returning significantly increased the contents of soil organic matter, total phosphorus, and available phosphorus by 31.20-32.75 g·kg-1, 0.11-0.18 g·kg-1, and 29.69-35.09 mg·kg-1, respectively. In conclusion, the application of Bacillus in the sand-blown area with a high-volume straw returning can notably improve the contents of soil organic matter and phosphorus components, the functional activity of bacteria, and the abundance of beneficial bacteria, which is of great significance to the rapid improvement of soil fertility in the middle- and low-yield fields in arid areas.

Warming promotes the decomposition of oligotrophic bacterial-driven organic matter in paddy soil

The ongoing global warming is causing paddy soil to come under threat by hitherto unseen levels of carbon and nitrogen loss. The mechanism of soil organic matter (SOM) components and microbial metabolism responding to increased temperature is complicated; for example, the temperature sensitivity (Q10) of SOM decomposition in rice topsoil and subsoil remains poorly understood. In this study, 0–30 cm columns of undisturbed paddy soil were collected and incubated at 5, 15, or 25 °C for 117 days to investigate the effect of temperature on SOM decomposition and microbial characteristics in different soil layers. Results showed that Q10 of subsoil (15–30 cm) was more than twice that of topsoil (0–15 cm), indicating that SOM mineralisation in subsoil was facilitated more by temperature than that in topsoil. Warming promoted the decomposition of recalcitrant SOM and reduced the fluorescent intensity of dissolved organic matter. Increased temperature exerted no significant effect on microbial biomass, but it did enhance the relative abundance of oligotrophic bacteria and promote anabolism. Therefore, recalcitrant SOM decomposition driven by oligotrophic bacteria was more sensitive to warming than labile organic matter consumption mediated by copiotrophic bacteria. Our findings revealed the underlying mechanisms by which elevating temperature promoted SOM mineralisation, thereby emphasising the need to remain vigilant regarding the threat to carbon dynamics in deep soil poised by global climate changes.

Thirty years of increased precipitation modifies soil organic matter fractions but not bulk soil carbon and nitrogen in a mesic grassland

Grassland ecosystems, which are known to be sensitive to climate change, have shown minimal responses of soil carbon (C) and nitrogen (N) pools to increased moisture availability, despite moisture-induced changes in plants and soil microbes (e.g., expected drivers of soil C and N). However, it is not clear if this apparent limited response is due to an unresponsive belowground system or because alterations in multiple soil organic matter (SOM) component pools and fluxes offset each other. To investigate potential responses of C and N in SOM to decadal increases in precipitation, we sampled soils from a 30-year precipitation augmentation experiment in an annually burned mesic grassland. We measured C and N in three SOM fractions which vary in their plant and microbial controls 1) free particulate OM (fPOM), 2) occluded POM plus heavy, coarse OM (oPOM + hcOM), and 3) mineral-associated OM (MAOM), as well as amino sugars, pyrogenic C and N, and root quality metrics. We found no changes in bulk C or N under increased precipitation, but SOM fractions were modified. Altered plant inputs and soil N availability appeared to drive the responses of fPOM N and oPOM + hcOM C:N, which were increased and decreased, respectively, by increased precipitation. In contrast, the observed increase in MAOM C and N under increased precipitation could not be connected to a specific driver, suggesting additional plant, microbial, or mineral measurements may be required. Regardless, our results indicate that investigating SOM fractions may more directly connect soil C and N pools and their drivers, compared to measuring only bulk SOM. Further, our finding of greater stable OM (MAOM) under increased precipitation suggests soil C storage could provide a negative feedback to climate change with increased moisture availability, but the lack of bulk SOM response suggests that this feedback is not strong in mesic grasslands.

Roles of Natural Phenolic Compounds in Polycyclic Aromatic Hydrocarbons Abiotic Attenuation at Soil-Air Interfaces through Oxidative Coupling Reactions.

Little information is available on the roles of natural phenolic compounds in polycyclic aromatic hydrocarbons (PAHs) attenuation at dry soil-air interfaces. The purpose of this study was to determine the roles of model phenolic constituents of soil organic matter (SOM) on the abiotic attenuation of PAHs. The phenolic compounds can significantly change the attenuation rates of PAHs, among which hydroquinone was the most effective in promoting anthracene and benzo[a]anthracene attenuation. Product identification and sequential extraction experiments revealed hydroquinone enhanced the formation of oxidative coupling products and promoted the incorporation of PAHs into humic analogues, thereby reducing potential risks to humans and ecosystems. Electron paramagnetic resonance spectroscopy analyses showed both PAHs and phenolic compounds could donate electrons to Lewis acid sites of soil minerals, resulting in the generation of persistent free radicals (PFRs). PFRs could promote the generation of ·OH to enhance PAH oxidation and could cross-couple with PAHs, resulting in high-molecular-weight oxidative coupling products. This study revealed for the first time the reaction mechanism between PAHs and phenolic components of SOM under relatively dry conditions and provided new insights into promoting PAHs detoxification in soils but also a potential strategy to increase the organic carbon sequestration.

Soil Micro-eukaryotic Diversity Patterns Along Elevation Gradient Are Best Estimated by Increasing the Number of Elevation Steps Rather than Within Elevation Band Replication.

The development of high-throughput sequencing (HTS) of environmental DNA (eDNA) has stimulated the study of soil microbial diversity patterns and drivers at all scales. However, given the heterogeneity of soils, a challenge is to define effective and efficient sampling protocols that allow sound comparison with other records, especially vegetation. In studies of elevational diversity pattern, a trade-off is choosing between replication within elevation bands vs. sampling more elevation bands. We addressed this question for soil protists along an elevation gradient on Mt. Asahi, Hokkaido, Japan. We compared two sampling approaches: (1) the replicate strategy (five replicates at six elevational bands, total = 30) and (2) the transect strategy (one sample in each of 16 different elevational bands). Despite a nearly twofold lower sampling effort, the transect strategy yielded congruent results compared to the replicate strategy for the estimation of elevational alpha diversity pattern: the regression coefficients between diversity indices and elevation did not differ between the two options. Furthermore, for a given total number of samples, gamma diversity estimated across the entire transect was higher when sampling more elevational bands as compared to replication from fewer elevational bands. Beta diversity (community composition turnover) was lower within a given elevational band than between adjacent bands and increased with elevation distance. In redundancy analyses, soil organic matter-related variable (the first principal component of soil organic matter, water content, total organic carbon, and nitrogen by whom were highly correlated) and elevation best explained elevational beta diversity pattern for both sampling approaches. Taken together, our results suggest that sampling a single plot per elevation band will be sufficient to obtain a good estimate of soil micro-eukaryotic diversity patterns along elevation gradients. This study demonstrated the effectiveness of the transect strategy in estimating diversity patterns along elevation gradients which is instructive for future environmental or even experimental studies. While not advocating for completely replacing replication-based sampling practices, it is important to note that both replicate and transect strategies have their merits and can be employed based on specific research goals and resource limitations.

Soil metabolomics: A powerful tool for predicting and specifying pesticide sorption

Sorption regulates the dispersion of pesticides from cropped areas to surrounding water bodies as well as their persistence. Assessing the risk of water contamination and evaluating the efficiency of mitigation measures, requires fine-resolution sorption data and a good knowledge of its drivers. This study aimed to assess the potential of a new approach combining chemometric and soil metabolomics to estimate the adsorption and desorption coefficients of a range of pesticides. It also aims to identify and characterise key components of soil organic matter (SOM) driving the sorption of these pesticides. We constituted a dataset of 43 soils from Tunisia, France and Guadeloupe (West Indies), covering extensive ranges of texture, organic carbon and pH. We performed untargeted soil metabolomics by liquid chromatography coupled with high-resolution mass spectrometry (UPLC-HRMS). We measured the adsorption and desorption coefficients of three pesticides namely glyphosate, 2,4-D and difenoconazole for these soils. We developed Partial Least Square Regression (PLSR) models for the prediction of the sorption coefficients from the RT-m/z matrix and conducted further ANOVA analyses to identify, annotate and characterise the most significant constituents of SOM in the PLSR models. The curated metabolomics matrix yielded 1213 metabolic markers. The prediction performance of the PLSR models was generally high for the adsorption coefficients Kdads (0.3 < R2 < 0.8) and for the desorption coefficients Kfdes (0.6 < R2 < 0.8) but low for ndes (0.03 < R2 < 0.3). The most significant features in the predictive models were annotated with a confidence level of 2 or 3. The molecular descriptors of these putative compounds suggest that the pool of SOM compounds driving glyphosate sorption is reduced compared to 2,4-D and difenoconazole, and these compounds are generally more polar. This approach can provide estimates of the adsorption and desorption coefficients of pesticides, including polar pesticide, for contrasted pedoclimates.

Two-Dimensional Correlation IR Spectroscopy of Humic Substances of Chernozem Size Fractions of Different Land Use

Diffuse reflectance FTIR measurements with two-dimensional correlation spectroscopy (2D-COS) are used for accurate band identification of chernozem comprising soil organic matter (SOM), including humic substances and mineral silicate matrix. Samples of different land use (native steppe, shelterbelt, bare fallow, and arable land) of a long-term field experiment were compared. Homospectral 2D-COS maps for size fractions obtained by wet fractionation were built, and the fraction size was used as a correlation-building variable (external perturbation) of 2D-COS. Synchronous 2D-COS maps are characterized by main correlation regions at 4000–3600 (hydrogen bonds), 1800–1150 (SOM), and 1100–200 cm−1 (quartz matrix). SOM range can be used as a signature of the samples distinguishing two pairs, native steppe–bare fallow and arable land–shelterbelt, by correlations at 1340–1320 cm−1 (CH2) and 1670 cm−1 (aromatic –C=C–). Asynchronous 2D-COS maps show bands at 3690–3620, 2930–2830, in the range of 1640–1250 (8 bands), 1160, 1070, 797, 697, 505, and 400 cm−1, the latter 5 indicate the increasing proportion of silicate to quartz in small fractions. The manifestation of asynchronous correlation bands at 1650, 1580–1560, 1444, 1340, and 1250 cm−1, which have no major contribution from inorganic soil components, are due to carbonyl, carboxylate, and aromatic C–C; their appearance order (accumulation of corresponding substances in larger factions) is different for each land use. The proposed approach provides the identifying SOM components with enough reliability for SOM IR bands that are weaker compared to mineral matrix bands in original IR spectra.

Cover Image

Ecology LettersVolume 26, Issue 5 p. ii-ii COVER IMAGEFree Access Cover Image First published: 12 April 2023 https://doi.org/10.1111/ele.14047AboutPDF Comments ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Graphical Abstract The cover image is based on the Letter Molecular 14c evidence for contrasting turnover and temperature sensitivity of soil organic matter components by Juan Jia et al., https://doi.org/10.1111/ele.14204. Comments Please enable JavaScript to view the comments powered by Disqus. Volume26, Issue5May 2023Pages ii-ii RelatedInformation

Compositional changes in the humin fraction resulting from the long-term cultivation of an Irish grassland soil: Evidence from FTIR and multi-NMR spectroscopies

Soil humin (HN), a major long-term sink for carbon in the pedosphere, plays a key role in the global carbon cycle, and has been less extensively studied than the humic and fulvic acids components. There are increasing concerns about the depletions of soil organic matter (SOM) arising from modern soil cultivation practices but there has been little focus on how HN can be altered as the result. This study has compared the HN components in a soil under cultivation for wheat for >30 years with those from an adjacent contiguous soil that had been under long-term grass for all that time. A urea-fortified basic solution isolated additional humic fractions from soils that had been exhaustively extracted in basic media. Then further exhaustive extractions of the residual soil material with dimethyl sulfoxide, amended with sulphuric acid isolated what may be called the “true” HN fraction. The long-term cultivation resulted in a loss of 53 % soil organic carbon in the surface soil. Infrared and multi-NMR spectroscopies showed the “true” HN to be dominated by aliphatic hydrocarbons and carboxylated structures, but with clear evidence for lesser amounts of carbohydrate and peptide materials, and with weaker evidence for lignin-derived substances. These lesser-amount structures can be sorbed on the soil mineral colloid surfaces and/or covered by the hydrophobic HN component or entrained within these which have strong affinities for the mineral colloids. HN from the cultivated site contained less carbohydrate and more carboxyl groups suggesting slow transformations took place resulting from the cultivation, but these were much slower than for the other components of SOM. It is recommended that a study be made of the HN in a soil under long-term cultivation for which the SOM content has reached a steady state and where HN will be expected to dominate the components of SOM.

Microbial necromass under global change and implications for soil organic matter.

Microbial necromass is an important source and component of soil organic matter (SOM), especially within the most stable pools. Global change factors such as anthropogenic nitrogen (N), phosphorus (P), and potassium (K) inputs, climate warming, elevated atmospheric carbon dioxide (eCO2 ), and periodic precipitation reduction (drought) strongly affect soil microorganisms and consequently, influence microbial necromass formation. The impacts of these global change factors on microbial necromass are poorly understood despite their critical role in the cycling and sequestration of soil carbon (C) and nutrients. Here, we conducted a meta-analysis to reveal general patterns of the effects of nutrient addition, warming, eCO2 , and drought on amino sugars (biomarkers of microbial necromass) in soils under croplands, forests, and grasslands. Nitrogen addition combined with P and K increased the content of fungal (+21%), bacterial (+22%), and total amino sugars (+9%), consequently leading to increased SOM formation. Nitrogen addition alone increased solely bacterial necromass (+10%) because the decrease of N limitation stimulated bacterial more than fungal growth. Warming increased bacterial necromass, because bacteria have competitive advantages at high temperatures compared to fungi. Other global change factors (P and NP addition, eCO2 , and drought) had minor effects on microbial necromass because of: (i) compensation of the impacts by opposite processes, and (ii) the short duration of experiments compared to the slow microbial necromass turnover. Future studies should focus on: (i) the stronger response of bacterial necromass to N addition and warming compared to that of fungi, and (ii) the increased microbial necromass contribution to SOM accumulation and stability under NPK fertilization, and thereby for negative feedback to climate warming.

Elucidating the composition of organic matter in water-repellent forest soils using analytical pyrolysis combined with gas chromatography–mass spectrometry (Py-GC–MS)

Soil water repellency (SWR) is an inability of soil to spontaneously absorb water. It affects the spatial distribution of soil moisture, may cause formation of preferential flow, increase surface runoff and the risk of water erosion, or affect nutrient availability for crops. Although there is a general agreement among published data that SWR is caused by hydrophobic components of soil organic matter (SOM), more comprehensive information is needed. Additionally, the link between SWR occurrence and SOM genesis has not been studied sufficiently. In this work, we analyzed SOM in water-repellent soils by pyrolysis combined with gas chromatography and mass spectrometry (Py-GC–MS). The samples were taken from two forest ecosystems in Slovakia: relatively dry pine–oak forest, located in the Záhorská nížina lowland (Záhorie), and spruce forest in the High Tatras with a colder and more humid climate. The results showed that the composition of SOM at both sites is dominated by partially decomposed residues of plant biomass. Whereas most compounds detected in the Záhorie samples were identified as pyrolysis products of lignin, the pyrolysates of the High Tatras soils originated mainly from polysaccharide-like substances. Although lauric (12:0), myristic (14:0) and palmitic (16:0) fatty acids were detected in pyrograms of water-repellent samples, the results suggest that the residues of lignin decomposition may contribute to SWR as well. Pyrolysates such as methylguaiacol, vinylguaiacol, dimethylphenol, or the methyl ester of vanillic acid are examples of less polar lignin-like moieties. Py-GC–MS data, as well as other soil properties, suggest that SWR at both sites is associated with the accumulation of certain SOM components in the topsoil. Acidic pH, higher C/N ratio and coarse soil texture prevent organic carbon stabilization in the studied soils. As a result, SOM is in great part composed of accumulated particulate residues with lignin-like origin and lipidic coatings, which contribute to SWR development during drier conditions.