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Article

Spectral Characteristics of Dissolved Organic Matter in Farmland Soils around Urumqi, China

by
Jianhua Zhu
1,
Jia Duo
2,3,*,
Zizhao Zhang
4,
Liang Pei
2,3,*,
Wenfeng Li
2,3 and
Rehemanjiang Wufuer
2,3
1
Geological Environment Monitoring Institute of Xinjiang Uygur Autonomous Region, Urumqi 830091, China
2
Xinjiang Key Laboratory of Environmental Pollution and Bioremediation, Xinjiang Institute of Ecology and Geography, Chinese Academy of Sciences, Urumqi 830011, China
3
National Engineering Technology Research Center for Desert-Oasis Ecological Construction, Xinjiang Institute of Ecology and Geography, Chinese Academy of Sciences, Urumqi 830011, China
4
School of Geology and Mining Engineering, Xinjiang University, Urumqi 830046, China
*
Authors to whom correspondence should be addressed.
Toxics 2023, 11(4), 376; https://doi.org/10.3390/toxics11040376
Submission received: 2 February 2023 / Revised: 6 April 2023 / Accepted: 7 April 2023 / Published: 16 April 2023
(This article belongs to the Section Toxicity Reduction and Environmental Remediation)
Browse Figures
Versions Notes

Abstract

:
The dissolved organic matter (DOM) is one of the most sensitive indicators of changes in the soil environment, and it is the most mobile and active soil component that serves as an easily available source of nutrients and energy for microbes and other living organisms. In this paper, DOM structural characteristics and main properties were investigated by three-dimensional fluorescence spectroscopy (EEM) and UV–visible spectrum technology in the farmland soils around Urumqi of China, and its possible sources and pathways were analyzed by spectroscopic indices. The results showed that humic-like substances were the main composition of the soil DOM, and its autogenesis characteristics were not obvious. Main DOM properties such as aromatability, hydrophobicity, molecular weight, molecular size, and humification degree in the southern region of Urumqi were higher than those of the northern region of Urumqi and Fukang in China, and higher on the upper layers of the soil (0–0.1 and 0.2 m) than in the deeper layer (0.2–0.3 m).This may be because the tilled layer is more subjected to fertilization and conducive to microbial activities. The spectroscopic analysis showed that the source of DOM of these regions is mainly from microbial metabolites. These results provide basic scientific data for the further research on the environmental chemical behavior of pollutants and pollution control in this region.

1. Introduction

Dissolved organic matter (DOM) is composed of humic acid, fulvic acid, and other organic materials which have abundant biological elements such as nitrogen, carbon, and phosphorus, and which exist extensively in various water, soil, and sediment environments [1,2]. It is closely related to the microbial metabolic process and the biological, chemical, and physical properties of the soil [3]. Soil DOM constitutes a rather small part of the soil organic matter, but it is the most mobile and active soil component, which can indicate the changes in soil processes and serve as a nutrient and energy source for microorganisms [3,4,5,6]. More importantly, DOM has influence on the soil negative charge denitrification process and acid-based reactions in the soil solution, and plays an important role in the biogeochemical carbon cycle [3]. Soil DOM has a wide range of sources [7,8], such as plant and animal residues, plant secretions, and industrial and agricultural organic wastewater [9,10,11].
Different DOM components in soil play an important role in agricultural production. DOM contains organic molecular mixtures with different structures and molecular weights, except nutrients such as C, N and P, for the growth of crops [9,12]. They contain many kinds of active functional groups, which affect soil fertility and microbial activities through different pathways [13]. Humic acid in soil DOM can greatly enhance the respiration of plants, improve the permeability of cell membranes of plants, and facilitate the absorption of nutrients by plants [14]. The organic colloid in soil DOM with a large number of negative charges has strong adsorption capacity [15]. Consequently, the cation exchange and water absorption capacity can be increased by several times or even tens of times in the clay particles by adsorbing a large number of cations and water [16,17]. These indicate that some components in soil DOM can play a significant role in improving soil fertility and buffering the soil acid–base balance. The humus in soil DOM has strong complexation ability and combines with environmental pollutants, such as potentially toxic elements, polycyclic aromatic hydrocarbons, pesticides, polychlorinated biphenyls, and herbicides, which affects their migration, toxicity, and bioavailability [18,19,20]. Therefore, understanding chemical characteristics of DOM in farmland soil could help us to better understand the transfer of major elements, nutrients, and water within farmland environments.DOM of autochthonous and allochthonous origins differ in properties and biogeochemical behavior. Allochthonous DOM may drive shifts in microbial community composition, whereas autochthonous DOM seems to affect the microbial community composition only transiently [21,22]. Therefore, the source of DOM should be given more attention in the farmland. The unique climate features, as well as low levels of water and nutrients, make the semi-arid regions prone to desertification [23]. To reveal the composition and source of farmland soil DOM will be particularly important in the arid regions of Northwest China due to the challenges of water deficiency, low water utilization rate, and low fertility in soil. DOM information is of particular importance for climate-sensitive soil ecosystems such as arid regions.
Joint use of multiple techniques to measure DOM properties is necessary as no single technique is capable of fully characterizing DOMs [24,25]. At present, spectrum, chromatography, energy spectrum, mass spectrum, and other characterization technologies have been gradually developed to characterize DOM properties and components [26,27,28]. Among them, spectral technology, due to its simple operation, is widely used to obtain DOM information such as aromatability, molecular weight, humification index, fluorescence components, and molecular spatial configuration [29,30,31]. In this study, three-dimensional fluorescence spectroscopy coupled with UV–visible spectrum technology were used to characterize the structural composition and important properties such as hydrophobicity, aromatability, molecular weight, and polarity of the farmland soil DOM around Urumqi city, and its sources and pathways were analyzed by spectroscopic indices.
Over the past several decades, the content, structure, and source of soil DOM have been widely investigated [9,10,12,32]. The majority of those studies have focused on forest soils, wetlands, sediments, and water [33,34]. Less attention has been paid to farmland soil DOM, particularly in arid and semi-arid regions. Serious soil erosion and salinization have made the scarcity of the limited arable land resources increasingly prominent in these regions. Therefore, further studies are still necessary to explore DOM composition and sources in farmland of arid and semi-arid regions. We need to better understand how DOM components vary and which site factors exert the greatest influence on DOM dynamics in farmland of this region, given the importance of DOM to biogeochemical cycles of farmland ecosystems. In this study, the important structural properties, its sources, and pathways of the farmland soil DOM around Urumqi of China were analyzed by spectroscopic indices in order to provide a scientific basis for understanding the migration and transformation processes of potentially toxic pollutants in the farmland of arid and semi-arid regions. More importantly, the researching results can provide important geochemical evidence for rational agricultural programming, planting, soil improvement, and scientific fertilization in the arid regions of Northwest China.

2. Materials and Methods

2.1. Site Description

Urumqi, the capital of the Xinjiang Uygur Autonomous Region, China, is located in the arid region of Northwest China and the center of the Eurasian continent, with an average altitude of 800 m. The geographic coordinates of the city are 86°37′33″–88°58′24″ E, 42°45′32″–44°08′00″ N [35]. The city belongs to the semi-arid temperate continental climate with an annual average precipitation of 2100 mm and an annual mean temperature of 7.3 °C. The topography is complex, and the terrain slopes downward from the south to the north and extends along the rivers in a zonal pattern. According to the third national land survey in 2019, Urumqi has 71,382.8 hectares of farmland. The area of high-quality farmland is about 46,960 hectares and is concentrated on the alluvial plain along Urumqi River and Toutun River. They are mainly distributed in Liushihu and Qinggeda lake townships in Xinshi District, Yangmaogong town and Changshanzi town in Midong district, Donggou township and Xigou township in Dabancheng District, Yongfeng township, Banfanggou township, and Shuixigou town in Urumqi County. Our sample collection is distributed in these districts, as shown in Figure 1 and Table 1.

2.2. Site Investigation and Sample Collection

The sampling was conducted in autumn, 2019.Three study areas around Urumqi city (northern Urumqi, southern Urumqi, and Fukang) were chosen with different soil properties and crops types. As shown in Figure 1, soil samples of 19 crop types were collected and marked 1S (Site 1)–19S (Site 19), respectively. The crops in the northern Urumqi region are mainly sweet potatoes, corn, cotton, and greenhouse vegetables. The crops in the southern Urumqi region are mainly potatoes, onion, flowers, and greenhouse vegetables. The crops in Fukang are mainly cotton and corn. Soil samples were collected with a 7.5-cm-diameter auger at each sampling site. We randomly collected 5 samples with an S-shaped pattern in each farmland and mixed them into a single sample. A total of 57 soil samples were collected from 19 agricultural land sites at different layers (0–0.1, 0.1–0.2, and 0.2–0.3 cm). All soil samples were immediately transported to the laboratory, and visible residues and roots were removed manually before passing them through a 2 mm sieve. Soil samples were then stored in a refrigerator (<4 °C) to measure the characteristics of the dissolved organic matter (DOM) in the soil.

2.3. DOM Extraction in Soil

The DOM extraction of soil samples was carried out by the soil and water vibration method. The collected soil samples were dried, grounded, and screened through 80 mesh for later use. A mass of 3.00 g of the treated soil sample was accurately weighed into a 250 mL conical flask, followed by the addition of 30 mL of ultra-pure water to adjust the ratio of soil to water to 1:10. The samples were placed in a constant temperature shaker for 18 h (25 °C, 200 r·min−1) and transferred to 50mL centrifuge tubes. After being centrifugated at 5000 r·min−1 for 10 min, the supernatant was taken and filtered through a 0.45 μm filter membrane to obtain the DOM solution of the soil samples, and was stored in a refrigerator at 4 °C for further analysis within 7 days [36].

2.4. Spectroscopic Analyses

F-7000 molecular fluorescence spectrometer (Hitachi, Japan) was used to detect the fluorescence characteristics of the DOM of the soil samples. The scanning speed was 1200 nm·min−1, and the scanning spectrum instrument was automatically corrected. The fluorescence spectrophotometer scanned over an excitation range of 200–500 nm at 5 nm intervals and an emission range of 200–550 nm at 5 nm intervals. The temperature of the reaction system was 22 °C, and the deionized water blank was subtracted from the measured results. A Shimadzu UV-3600 photometer was used to determine the UV–visible spectrum of the DOM, scanning over an excitation range of 200–500 nm at 1 nm intervals. Ultrapure water was used as the blank. All tests were repeated three times, and typical spectra are shown from one of the triplicate examinations.

2.5. Spectroscopic Indices and Data Analysis

General features and three optical indices were used to further describe the compositional characteristics of soil DOM based on the corrected absorbance and EEM fluorescence data. SUVA254, SUVA260, and SUVA280 are the absorption coefficients of unit DOC concentrations at wavelength 254 nm, 260 nm, and 280 nm, and they are used to characterize the aromaticity, hydrophobicity, and molecular weight of DOM molecules, respectively [37,38]. A250/A365 is the absorbance ratio at 250 and 365 nm and is used to estimate the size of DOM molecules. A300/A400 is the absorbance ratio at wavelengths 300 and 400 nm and is used to characterize the humification degree of DOM molecules [39]. Fluorescence index (FI), the ratio of the emission intensity at 450 nm–500 nm, is used to reflect the relative microbial (>1.9) or terrestrial plant contribution (<1.4) [40]. Biological index (BIX) is an indicator of the relative contribution of the recently microbially produced DOM, calculated as the ratio of emission intensity at 380–430 nm [41].
Averages and standard deviations were determined using Excel 2020 (Microsoft Office 2020; Microsoft, Redmond, WA, USA). The figures were drawn using Origin 9.0.

2.6. Quality Assurance and Quality Control

In order to guarantee the accuracy of our results, a series of quality assurance and quality control (QA/QC) measures were taken during the process from field sampling to laboratory analysis. Three mixed soil samples were collected in each farmland. All flasks and beakers used in the experiment were washed three times with deionized water. All tests were repeated three times, and every 20 samples were used to measure one standard sample. The t-test statistical method was applied to determine whether there were significant differences among different groups. The significance level for the analysis was set at p < 0.05. The blank controls were produced using the same processing methods as those applied to the field samples and in laboratory process.

3. Results and Discussion

3.1. Fluorescence Characteristics of Soil DOM

The practice of 3D fluorescence spectroscopy has the advantages of requiring fewer samples, high sensitivity, and no damage to the sample structure. Compared with conventional fluorescence spectroscopy analysis, it can obtain more comprehensive DOM component information by simultaneously scanning excitation and emission wavelengths to form fluorescence excitation–emission spectral matrix (EEMS). DOM can be divided into six categories according to the different positions of fluorescence peaks. Peak A (Ex/Em = 230–260 nm/370–460 nm) represents fulvic-like substances in the ultraviolet region, which is mainly caused by some organic substances with small molecular weight and high fluorescence efficiency. The peak C (Ex/Em = 310–360 nm/370–480 nm) represents the visible light region, and it is mainly produced by organic substances with relatively stable and large molecular weight. The A and C peaks may be related to carbonyl and carboxyl groups in DOM and generally indicate exogenous inputs. Peak D (Ex/Em = 350–440 nm/430–510 nm) and F (Ex/Em = 280–288 nm/420–450 nm) represents soil humic acids, which can be used to characterize the humification degree of DOM. Peak B (Ex/Em = 225–230 nm/305–310 nm) and peak T (Ex/Em = 225–230 nm/320–350 nm) represents tyrosine-like and tryptophan-like substances, respectively, which are mainly produced by organic substances with relatively stable and large molecular weight. Fluorescence peaks B and T belong to protein-like peaks, which are usually associated with microbial decomposition [36,42,43].
In this study, the fluorescence emission spectrum of the S2 sample was chosen to represent those of the north Urumqi region and Fukang, while the S14 sample was chosen to represent that of the south Urumqi region (Figure 2) according to the regional similarity features of the soil samples. The results of the fluorescence analysis showed similar peak shapes of obvious fluorescence peaks of A and D with a weak peak T in the soil DOM of the southern and northern regions of Urumqi and the Fukang region. It indicated that the DOM components of the farmland soil around Urumqi were mainly fulvic acids in the ultraviolet region, and there was lower content of soil humic acids and protein-like peak groups. The fluorescence peaks of the soil samples at different depths showed that there were only differences in fluorescence intensity without obvious difference in the peak types. The fluorescence intensity of the 0–0.1 m and 0.1–0.2 m soil samples was higher than that of the 0.2–0.3 m soil samples, probably due to the fact that the upper tilled layers of the soil contain a higher content of organic matter with higher fertility. Moreover, the root system of the crops is concentrated in 0–0.2 m layer, which may also lead to the higher fluorescence intensity in the upper layers of the soil than in the deeper layers. Further, comparing the mean fluorescence intensity in different regions (Figure 3), we found that the mean fluorescence intensity in Fukang was higher than that in the other two regions, and the mean fluorescence intensity in Fukang and the northern region of Urumqi was attenuated with soil depth, while the intensity in thesouthern part of Urumqi did not change significantly. This might be attributed to the fact that agricultural activities in the north part of Urumqi and the Fukang region are more intensive, with frequent interference, which led to more exogenous DOM in the soil, while the south part of Urumqi is mostly fallow land with much less interference, which might be the main cause of the relatively stable fluorescence intensity in this region.
The fluorescence index (FI) often indicates the sources of DOM. Generally, there are two main sources of plant and microbial metabolites with FI values of 1.4 and 1.9, respectively [40,41]. When FI < 1.4, DOM is mainly from plant sources. When FI is between 1.4 and 1.9, DOM is from both plant and microbial metabolites. While FI > 1.9, DOM is dominated by microbial metabolite sources (such as tyrosine and tryptophan) [44]. In this study, as shown in Figure 4, the FI index of farmland soil DOM in the south of Urumqi and the north of Urumqi were almost higher than 1.9, indicating that DOM in these farmland soil samples mainly came from microbial metabolites [43]. The FI index of Fukang was greater than 1.4, indicating that the DOM source of Fukang farmland soil was not only microbial metabolites but also plant metabolites. There was no significant FI difference in different soil layers.
The autogenesis index (BIX) is an important index reflecting the characteristics of DOM autogenesis. When the BIX > 1, it indicates that DOM is mainly autogenic. When the BIX < 1, it indicates that DOM autogenic features are not obvious [39]. As can be seen from Figure 4, the BIX of DOM of 19 soil samples was almost less than 1, and the BIX of DOM of individual samples in Fukang was greater than 1. Therefore, it suggested that most samples did not have obvious autogenesis characteristics. They showed low bioavailability and less protein-like components, which also precisely explain why the protein-like peak was not obvious in the three-dimensional fluorescence spectrum of soil DOM.

3.2. UV–Vis Spectral Characteristics of Soil DOM

The nature of DOM determines the environmental effects of DOM. In addition, understanding the structural composition and main properties of DOM helps to understand the interaction between DOM and geochemical elements and pollutants. Hydrophobicity, aromatability, molecular weight, polarity, and material composition are the important properties of DOM.UV–Vis spectroscopy has the advantages of high sensitivity and lower sample requirements, and it is widely used to characterize these properties of soil DOM. Aromatability and hydrophobicity are important characterization indexes for qualitative descriptions of DOM [45]. Generally, a more aromatic and hydrophobic DOM demonstrates a stronger binding capacity with hydrophobic organic pollutants [44]. SUVA254 is usually used to characterize the aromaticity of DOM molecules, and higher values means greater aromaticity. As shown from Table 2, SUVA254 of soil DOM in our study area ranged from 0.94 to 3.07, and the aromaticity of the soil DOM was in the order of south of Urumqi > north of Urumqi > the Fukang region, with significant differences. However, the SUVA254 of 0–0.1 and 0.1–0.2 m soil layers was slightly higher than that of the 0.2–0.3 m soil layer, without significant differences.
The content of hydrophobic components of DOM molecules is generally defined as SUVA260 [46]. Higher SUVA260 indicates greater hydrophobic components. Table 2 shows that the range of SUVA260 of all samples in the study area ranged from 0.92 to 3.12. The overall variation of hydrophobicity is consistent with the aromaticity of each layer. Hydrophobic components in the 0–0.1 m and 0.1–0.2 m soil layers are slightly higher than those in the 0.2–0.3 m soil layer. This might be due to the fact that hydrophobic components are easily adsorbed to the surface soil, while hydrophilic components migrate to the deep soil. The deeper the soil, the greater the water content. In the downward migration, some components form a complex with metal ions, and the hydrogen bonds in the complex may lead to the quenching phenomenon of fluorescent substances, resulting in the stronger fluorescence intensity in the surface than in the deep layer. SUVA260 of different regions in Table 2 showed that SUVA260 in the south of Urumqi was significantly higher than that of the other two regions at each depth, followed by the north of Urumqi and the Fukang region.
Molecular weight is also an important property of DOM. Substances with small molecular weight mainly include amino acids, fatty acids, aromatic acids, etc., while substances with high molecular weight include fulvic acid and humic acid, etc. SUVA280 is used to characterize the molecular weight of DOM molecules, and the higher the value, the greater the molecular weight [47]. SUVA280 of soil samples in each layer was shown in Table 2. In comparison, the molecular weight in 0–0.1 m and 0.1–0.2 m soil was greater than that of 0.2–0.3 m, which is consistent with the features of the aforementioned sail tilled layer. Organic matter in the tilled layer was more concentrated, and the root systems were well developed. According to Table 2, the average SUVA280 of the samples in the south of Urumqi was significantly higher than those in the other two regions, and followed by the north of Urumqi and the Fukang region.
SUVA250/SUVA365 is used to characterize the molecular size of DOM molecules. A smaller ratio means smaller but more DOM molecules [48]. As shown in Table 2, SUVA250/SUVA365 in 0–0.2 m layer was also higher than that in the 0.2–0.3 m layer, indicating that the main DOM molecules in the surface layer were macromolecules with lower content. The deeper the soil was, the higher the DOM content and the smaller the molecules were. According to Table 2, SUVA250/SUVA365 in the south of Urumqi was significantly higher than that of the other two regions, while there was an insignificant difference in the other two regions.
SUVA300/SUVA400 is used to characterize the humification degree of DOM molecules. When SUVA300/SUVA400 > 3.5, DOM is dominated by fulic acid, and while SUVA300/SUVA400 < 3.5, humic acid is dominant. It is generally believed that the higher the degree of humification is, the stronger the binding capacity DOM has with potentially toxic elements and organic pollutants [49]. Table 2 shows that the SUVA300/SUVA400 of all soil samples was between 1.18 and 2.10 (less than 3.5), indicating that the humification degree of all soil samples was not high in three regions, and DOM was dominated by humic acid. SUVA300/SUVA400 in the south of Urumqi was higher than that in the other two regions, and the degree of soil humification in Fukang and the north of Urumqi was not significantly different. Moreover, the humification degree of the 0–0.2 m layer was slightly higher than that of the 0.2–0.3 m layer, which was similar to the trend of molecular weight and molecular size.
In general, aromaticity, hydrophobicity, molecular weight, molecular size, and humification degree of soil DOM in all three regions showed a similar trend, and these features were more obvious in the south of Urumqi than in the north of Urumqi and Fukang. The reason might be that the south of Urumqi is located in the mountainous region, and most of the land has been fallow for many years with less human disturbance, which leads to relatively rich humus in soil. Moreover, the samples in the south of Urumqi were mainly collected from greenhouse vegetables and flowers. The amount of fertilizers and other organic chemicals used in greenhouse soils was greater compared to in the field. Fertilizers could increase the content of DOM in the surface soil, reduce the C/N ratio of DOM, and improve soil fertility and conjugated structure. Fertilizers can increase humificationdegree, aromatology, hydrophobicity, and average molecular weight, which is conducive to increasing microbial activity, crop litter, and root exudates, and accelerate the decomposition and transformation of soil organic compounds [21,39]. The samples in the north of Urumqi and Fukang were mainly collected from vegetable and cotton fields, and the soil quality has been deteriorated slightly after many years of cultivation.
Compared with DOM in the 0.2–0.3 m soil layer, DOMs in the 0–0.1 m and 0.1–0.2 m soil layers are more subjective to fertilization, because the decomposition process of organic materials mainly occurs in the surface layer. In addition, long-term input of organic materials increases the microbial activity of soil in the surface layer. In addition, there is a large amount of crop residues in the surface soil, which could enrich DOM in the surface soil to a certain extent. Combined with fluorescence analysis, the surface layer was dominated by macromolecular humic acid and fulvic acid, and the humification degree was higher than that in the deep layer. However, the humification degree and the DOM molecular richness of the whole region were still very low, which was closely related to the natural environmental conditions of the relatively low soil quality of overall Xinjiang.
Therefore, we demonstrated that microbial metabolites were the dominant DOM sources around Urumqi, which was supported by FI index. Microbially-derived DOM supported less diversity of soil bacteria compared to DOM coming from plant sources. This is largely because plants represent major resource inputs to soil, and can substantially diversify the pool of resources and offer more ecological niches to partition by generating plant residues and root exudates [37,48]. In addition, we noted that all samples had no obvious autogenesis characteristics according to the BIX index. This indicates that farmland in study area is environmentally fragile and has lower microbial diversity. Meanwhile, aromaticity, hydrophobic, molecular weight, molecular size, and humification degree of soil DOM in the south of Urumqi were better than that in the north of Urumqi and Fukang, further indicating that the aromatics, hydrophobicity, humification degree, and average molecular weight of soil DOM were increased by fertilization, which made it more stable [21,39]. These results further demonstrated that DOM quality is of key importance in affecting soil quality in arid and semi-arid regions. In addition, fertilization is one of the important measures of artificial intervention and effectively enhances organic matter content in soil.

4. Conclusions

In this study, three-dimensional fluorescence spectroscopy and UV–visible spectrum technology were applied to characterize the structural composition and important properties of the farmland soil DOM around Urumqi city. Spectroscopic indices were used to analyze its possible sources. The results showed that the composition of DOM in the surrounding area of Urumqi was mainly humic acid and fulvic acid macromolecules, with alower content of protein-like peak group substances. The autogenetic characteristics of DOM in the three regions were not obvious. The fluorescence excitation spectra of different crop types showed a similar trend with different intensity. The fluorescence intensity of DOM in the north Urumqi and Fukang areas decreased with the increase in soil depth, while the fluorescence intensity in the south was relatively stable. The DOM content in the south of Urumqi was higher than that in the north of Urumqi and Fukang, which might be due to the use of fertilizers or organic chemicals. The higher content of DOM in upper layers of the soil (0–0.1 and 0.1–0.2 m) than in the deeper layer (0.2–0.3 m) in all three regions was due to the fact that the soil tilled layer was more subjected to fertilization and conducive to microbial activities. Spectroscopic indices analysis further confirmed that the DOM of all three regions were mainly from microbial metabolites.

Author Contributions

J.D. conceived and designed the study; J.Z. collected and analyzed the data; and L.P. assisted with data analysis, and was mostly in charge of tables and figures; Z.Z. revised the manuscript; W.L. and R.W. collected the soil sample. All authors have read and agreed to the published version of the manuscript.

Funding

The authors gratefully acknowledge the financial support by the Science and Technology Support Project of the Xinjiang Uygur Autonomous Region (Grant No. 2022E02071; 2022B02041).

Institutional Review Board Statement

This study does not involve humans and animals.

Informed Consent Statement

This study does not involve any humans.

Data Availability Statement

This study does not report any data.

Acknowledgments

The authors would like to acknowledge the kind help and suggestions of all of the anonymous reviewers.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Gmach, M.R.; Cherubin, M.R.; Kaiser, K.; Pellegrino Cerri, C.E. Processes that influence dissolved organic matter in the soil: A review. Sci. Agric. 2020, 77, e20180164. [Google Scholar] [CrossRef]
  2. Peter, P.C. Soil Organic Matter/Carbon Dynamics in Contrasting Tillage and Land Management Systems: A Case for Smallholder Farmers with Degraded and Marginal Soils. Commun. Soil Sci. Plant Anal. 2017, 48, 2013–2031. [Google Scholar] [CrossRef]
  3. Smreczak, B.; Ukalska-Jaruga, A. Dissolved organic matter in agricultural soils. Soil Sci. Annu. 2021, 72, 132234. [Google Scholar] [CrossRef]
  4. Bowen, S.R.; Gregorich, E.G.; Hopkins, D.W. Biochemical properties and biodegradation of dissolved organic matter from soils. Biol. Fertil. Soils 2009, 45, 733–742. [Google Scholar] [CrossRef]
  5. Kaiser, K.; Kalbitz, K. Cycling downwards—Dissolved organic matter in soils. Soil Biol. Biochem. 2012, 52, 29–32. [Google Scholar] [CrossRef]
  6. Mitchell, P.J.; Simpson, A.J.; Soong, R.; Oren, A.; Chefetz, B.; Simpson, M.J. Solution-state NMR investigation of the sorptive fractionation of dissolved organic matter by alkaline mineral soils. Environ. Chem. 2013, 10, 333–340. [Google Scholar] [CrossRef]
  7. Bolan, N.S.; Adriano, D.C.; Kunhikrishnan, A.; James, T.; McDowell, R.; Senesi, N. Chapter One—Dissolved Organic Matter: Biogeochemistry, Dynamics, and Environmental Significance in Soils. In Advances in Agronomy; Sparks, D.L., Ed.; Elsevier Academic Press Inc.: San Diego, CA, USA, 2011; Volume 110, pp. 1–75. [Google Scholar]
  8. Bastida, F.; Moreno, J.L.; Hernández, T.; García, C. Microbiological activity in a soil 15 years after its devegetation. Soil Biol. Biochem. 2006, 38, 2503–2507. [Google Scholar] [CrossRef]
  9. Kaiser, K.; Guggenberger, G. Mineral surfaces and soil organic matter. Eur. J. Soil Sci. 2003, 54, 219–236. [Google Scholar] [CrossRef]
  10. Kalisz, B.; Lachacz, A.; Glazewski, R.; Grabowski, K. Labile organic carbon fractions after amendment of sandy soil with municipal sewage sludge and compost. J. Elem. 2017, 22, 785–797. [Google Scholar] [CrossRef]
  11. Willey, J.D.; Kieber, R.J.; Eyman, M.S.; Avery, G.B., Jr. Rainwater dissolved organic carbon: Concentrations and global flux. Glob. Biogeochem. Cycles 2000, 14, 139–148. [Google Scholar] [CrossRef]
  12. Rosa, E.; Debska, B. Seasonal changes in the content of dissolved organic matter in arable soils. J. Soils Sediments 2018, 18, 2703–2714. [Google Scholar] [CrossRef]
  13. Zsolnay, Á. Dissolved organic matter: Artefacts, definitions, and functions. Geoderma 2003, 113, 187–209. [Google Scholar] [CrossRef]
  14. Leinweber, P.; Jandl, G.; Baum, C.; Eckhardt, K.-U.; Kandeler, E. Stability and composition of soil organic matter control respiration and soil enzyme activities. Soil Biol. Biochem. 2008, 40, 1496–1505. [Google Scholar] [CrossRef]
  15. Avneri-Katz, S.; Young, R.B.; McKenna, A.M.; Chen, H.; Corilo, Y.E.; Polubesova, T.; Borch, T.; Chefetz, B. Adsorptive fractionation of dissolved organic matter (DOM) by mineral soil: Macroscale approach and molecular insight. Org. Geochem. 2017, 103, 113–124. [Google Scholar] [CrossRef]
  16. De Troyer, I.; Merckx, R.; Amery, F.; Smolders, E. Factors Controlling the Dissolved Organic Matter Concentration in Pore Waters of Agricultural Soils. Vadose Zone J. 2014, 13, vzj2013.2009.0167. [Google Scholar] [CrossRef]
  17. Brockett, B.F.T.; Prescott, C.E.; Grayston, S.J. Soil moisture is the major factor influencing microbial community structure and enzyme activities across seven biogeoclimatic zones in western Canada. Soil Biol. Biochem. 2012, 44, 9–20. [Google Scholar] [CrossRef]
  18. García-Gil, J.C.; Plaza, C.; Senesi, N.; Brunetti, G.; Polo, A. Effects of Long-Term Sewage Sludge Amendment on the Composition, Structure and Proton Binding Activity of Soil Fulvic Acids. CLEAN Soil Air Water 2007, 35, 480–487. [Google Scholar] [CrossRef]
  19. García-Gil, J.C.; Plaza, C.; Fernández, J.M.; Senesi, N.; Polo, A. Soil fulvic acid characteristics and proton binding behavior as affected by long-term municipal waste compost amendment under semi-arid environment. Geoderma 2008, 146, 363–369. [Google Scholar] [CrossRef]
  20. Luo, L.; Lin, S.; Huang, H.; Zhang, S. Relationships between aging of PAHs and soil properties. Environ. Pollut. 2012, 170, 177–182. [Google Scholar] [CrossRef] [PubMed]
  21. Jiang, T.; Kaal, J.; Liang, J.; Zhang, Y.; Wei, S.; Wang, D.; Green, N.W. Composition of dissolved organic matter (DOM) from periodically submerged soils in the Three Gorges Reservoir areas as determined by elemental and optical analysis, infrared spectroscopy, pyrolysis-GC-MS and thermally assisted hydrolysis and methylation. Sci. Total Environ. 2017, 603, 461–471. [Google Scholar] [CrossRef]
  22. Li, S.; Li, M.; Wang, G.; Sun, X.; Xi, B.; Hu, Z. Compositional and chemical characteristics of dissolved organic matter in various types of cropped and natural Chinese soils. Chem. Biol. Technol. Agric. 2019, 6, 20. [Google Scholar] [CrossRef]
  23. Huang, M.; Chai, L.; Jiang, D.; Zhang, M.; Jia, W.; Huang, Y.; Zhou, J. Dissolved organic matter (DOM) quality drives biogeographic patterns of soil bacterial communities and their association networks in semi-arid regions. Fems Microbiol. Ecol. 2021, 97, fiab083. [Google Scholar] [CrossRef] [PubMed]
  24. Barker, J.D.; Dubnick, A.; Lyons, W.B.; Chin, Y.P. Changes in Dissolved Organic Matter (DOM) Fluorescence in Proglacial Antarctic Streams. Arct. Antarct. Alp. Res. 2013, 45, 305–317. [Google Scholar] [CrossRef]
  25. Gbadegesin, L.A.; Tang, X.; Liu, C.; Cheng, J. Transport of Veterinary Antibiotics in Farmland Soil: Effects of Dissolved Organic Matter. Int. J. Environ. Res. Public Health 2022, 19, 1702. [Google Scholar] [CrossRef] [PubMed]
  26. Wang, M.; Liao, C.; Tian, Q.; Wang, D.; Wu, Y.; Tang, Y.; Liu, F. Dissolved Organic Matter Characteristics and Important Site Factors in a Subtropical Mountain Forest in Central China. For. Sci. 2020, 66, 49–57. [Google Scholar] [CrossRef]
  27. Zhao, X.; Hu, Z.; Yang, X.; Cai, X.; Wang, Z.; Xie, X. Noncovalent interactions between fluoroquinolone antibiotics with dissolved organic matter: A H-1 NMR binding site study and multi-spectroscopic methods. Environ. Pollut. 2019, 248, 815–822. [Google Scholar] [CrossRef]
  28. Rizzuto, S.; Baho, D.L.; Jones, K.C.; Zhang, H.; Leu, E.; Nizzetto, L. Binding of waterborne pharmaceutical and personal care products to natural dissolved organic matter. Sci. Total Environ. 2021, 784, 147208. [Google Scholar] [CrossRef]
  29. Wang, R.; Yang, S.; Fang, J.; Wang, Z.; Chen, Y.; Zhang, D.; Yang, C. Characterizing the Interaction between Antibiotics and Humic Acid by Fluorescence Quenching Method. Int. J. Environ. Res. Public Health 2018, 15, 1458. [Google Scholar] [CrossRef]
  30. Pan, B.; Wang, P.; Wu, M.; Li, J.; Zhang, D.; Xiao, D. Sorption kinetics of ofloxacin in soils and mineral particles. Environ. Pollut. 2012, 171, 185–190. [Google Scholar] [CrossRef]
  31. Fan, W.; Guo, T.; Gao, S.; Lu, Y.; Meng, Y.; Huo, M. Evolution of dissolved organic matter during artificial groundwater recharge with effluent from underutilized WWTP and the resulting facilitated transport effect. Environ. Res. 2021, 193, 110527. [Google Scholar] [CrossRef]
  32. Tunaley, C.; Tetzlaff, D.; Soulsby, C. Scaling effects of riparian peatlands on stable isotopes in runoff and DOC mobilisation. J. Hydrol. 2017, 549, 220–235. [Google Scholar] [CrossRef]
  33. Karavanova, E.I.; Belyanina, L.A.; Stepanov, A.A. Water-soluble organic matter and soil solution acidity in the main soil types of the central forest state biosphere reserve. Eurasian Soil Sci. 2007, 40, 493–504. [Google Scholar] [CrossRef]
  34. Nebbioso, A.; Piccolo, A. Molecular characterization of dissolved organic matter (DOM): A critical review. Anal. Bioanal. Chem. 2013, 405, 109–124. [Google Scholar] [CrossRef] [PubMed]
  35. Li, X.W.; Du, J.G.; Long, H.Y.; Sun, G.L. Characteristics and risk analysis of hydrological disaster events from 1949 to 2015 in Urumqi, China. Theor. Appl. Climatol. 2019, 137, 745–754. [Google Scholar] [CrossRef]
  36. Wang, Y.; Zhang, X.; Zhang, X.; Meng, Q.; Gao, F.; Zhang, Y. Characterization of spectral responses of dissolved organic matter (DOM) for atrazine binding during the sorption process onto black soil. Chemosphere 2017, 180, 531–539. [Google Scholar] [CrossRef]
  37. Ersan, M.S.; Liu, C.; Amy, G.; Karanfil, T. The interplay between natural organic matter and bromide on bromine substitution. Sci. Total Environ. 2019, 646, 1172–1181. [Google Scholar] [CrossRef]
  38. Comstock, S.E.H.; Boyer, T.H.; Graf, K.C.; Townsend, T.G. Effect of landfill characteristics on leachate organic matter properties and coagulation treatability. Chemosphere 2010, 81, 976–983. [Google Scholar] [CrossRef]
  39. Tang, G.; Wang, Q. Impact of environmental factors and tributary contributions on tidal dissolved organic matter dynamics. Chemosphere 2022, 308, 136384. [Google Scholar] [CrossRef]
  40. Coble, P.G. Characterization of marine and terrestrial DOM in seawater using excitation-emission matrix spectroscopy. Mar. Chem. 1996, 51, 325–346. [Google Scholar] [CrossRef]
  41. Musadji, N.Y.; Lemee, L.; Caner, L.; Porel, G.; Poinot, R.; Geffroy-Rodier, C. Spectral characteristics of soil dissolved organic matter: Long-term effects of exogenous organic matter on soil organic matter and spatial-temporal changes. Chemosphere 2020, 240, 124808. [Google Scholar] [CrossRef]
  42. Lv, J.; Dou, Y.; Gong, W.; Duan, X.; Hou, L.a.; Zhang, L.; Xi, B.; Yu, S. Characterization of Dissolved Organic Matter in Hybrid Constructed Wetlands Using Three-Dimensional Excitation-Emission Matrix Fluorescence Spectroscopy. J. Water Chem. Technol. 2019, 41, 113–118. [Google Scholar] [CrossRef]
  43. Zhang, Y.; Wang, Y.; Zhang, X.; Li, R.; Chen, Y.; Meng, Q. Investigating the behavior of binding properties between dissolved organic matter (DOM) and Pb(II) during the soil sorption process using parallel factor analysis (PARAFAC) and two-dimensional correlation spectroscopy (2D-COS). Environ. Sci. Pollut. Res. 2017, 24, 25156–25165. [Google Scholar] [CrossRef] [PubMed]
  44. Lin, Y.; Hu, E.; Sun, C.; Li, M.; Gao, L.; Fan, L. Using fluorescence index (FI) of dissolved organic matter (DOM) to identify non-point source pollution: The difference in FI between soil extracts and wastewater reveals the principle. Sci. Total Environ. 2023, 862, 160848. [Google Scholar] [CrossRef] [PubMed]
  45. Li, W.; Li, X.; Han, C.; Gao, L.; Wu, H.; Li, M. A new view into three-dimensional excitation-emission matrix fluorescence spectroscopy for dissolved organic matter. Sci. Total Environ. 2023, 855, 158963. [Google Scholar] [CrossRef]
  46. Zhang, X.; Li, Y.; Ye, J.; Chen, Z.; Ren, D.; Zhang, S. The spectral characteristics and cadmium complexation of soil dissolved organic matter in a wide range of forest lands. Environ. Pollut. 2022, 299, 118834. [Google Scholar] [CrossRef]
  47. Harman, B.I.; Koseoglu, H.; Yigit, N.O.; Sayilgan, E.; Beyhan, M.; Kitis, M. The removal of disinfection by-product precursors from water with ceramic membranes. Water Sci. Technol. 2010, 62, 547–555. [Google Scholar] [CrossRef]
  48. Engel, M.; Chefetz, B. The missing link between carbon nanotubes, dissolved organic matter and organic pollutants. Adv. Colloid Interface Sci. 2019, 271, 101993. [Google Scholar] [CrossRef]
  49. Song, N.; Wu, D.; Xu, H.; Jiang, H. Integrated evaluation of the reactive oxygen species (ROS) production characteristics in one large lake under alternating flood and drought conditions. Water Res. 2022, 225, 119136. [Google Scholar] [CrossRef]
Toxics 11 00376 g001 550
Figure 1. The Map of the sampling points.
Figure 1. The Map of the sampling points.
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Figure 2. Typical 3D-EEM spectra of soil DOM of sample sitein S2 and S14.
Figure 2. Typical 3D-EEM spectra of soil DOM of sample sitein S2 and S14.
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Figure 3. Average fluorescence intensities of different soil depth on different districts.
Figure 3. Average fluorescence intensities of different soil depth on different districts.
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Figure 4. FI (fluorescence index) and BIX (autochthonous index) of soil DOM on different districts.
Figure 4. FI (fluorescence index) and BIX (autochthonous index) of soil DOM on different districts.
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Table
Table 1. Characteristics of the sampling points.
Table 1. Characteristics of the sampling points.
SiteCoordinatesCrop TypesSoil TypespHDistricts
S187°583684′ E, 44°060206′ Nsweet potatoCamborthids 7.92The north of Urumqi
S287°644409′ E, 44°082329′ NcornCamborthids8.05
S387°551937′ E, 44°325629′ NcottonCamborthids8.32
S487°595882′ E, 44°121391′ Nsweet potatoCamborthids8.06
S587°565842′ E, 44°409290′ NcottonCamborthids8.39
S687°591934′ E, 44°153144′ NcornCamborthids8.09
S787°601204′ E, 44°171739′ NriceCamborthids7.93
S887°631674′ E, 44°283554′ NcottonCamborthids8.16
S987°479110′ E, 43°976233′ NspinachCamborthids7.96
S1087°472458′ E, 43°963415′ NwheatCamborthids8.07
S1187°584381′ E, 44°229457′ NpumpkinCamborthids8.07
S1287°402805′ E, 43°459628′ Ngreenhouse flowerCalciustoll7.56The south of Urumqi
S1387°282321′ E, 43°480383′ Ngreenhouse flowerCalciustoll7.68
S1487°390822′ E, 43°629482′ Ngreenhouse vegetableCalciustoll7.93
S1587°355654′ E, 43°597425′ NpotatoCalciustoll8.03
S1687°389653′ E, 43°682755′ NonionCalciustoll8.05
S1787°961693′ E, 44°339934′ NcottonQuartisamment8.36Fukang
S1888°474617′ E, 44°166691′ NcornQuartisamment8.40
S1988°303642’ E, 44°172170′ NcornQuartisamment8.51
Table
Table 2. The characteristics of UV spectra absorption of soil DOM on different districts (SUVA254, SUVA260, SUVA280, SUVA250/SUVA365, SUVA300/SUVA400).
Table 2. The characteristics of UV spectra absorption of soil DOM on different districts (SUVA254, SUVA260, SUVA280, SUVA250/SUVA365, SUVA300/SUVA400).
SiteSUVA254/L·(mg·m)−1SUVA260/L·(mg·m)−1SUVA280/L·(mg·m)−1SUVA250/SUVA365SUVA300/SUVA400District
0–0.1 m0.1–0.2 m0.2–0.3 m0–0.1 m0.1–0.2 m0.2–0.3 m0–0.1 m0.1–0.2 m0.2–0.3 m0–0.1 m0.1–0.2 m0.2–0.3 m0–0.1 m0.1–0.2 m0.2–0.3 m
S11.45521.49111.46061.57531.57801.51141.45881.46701.39271.46091.64301.59541.28201.38331.3666The north of Urumqi
S21.17311.12701.11381.24641.21391.19671.19581.16621.16101.42351.43471.39251.29361.28521.2567
S31.42951.29091.20821.37531.29801.22631.38601.27881.23241.56781.51791.46791.31961.30661.2775
S41.10231.13230.94881.08230.96740.92351.06351.01320.97211.55771.36231.30491.25551.21011.1836
S50.98930.97530.94611.00981.01100.96481.03531.03501.00251.38581.39491.35871.23501.23961.2360
S61.38781.33811.82801.34801.30331.83651.29781.27041.68151.63491.59741.86401.37631.36871.5065
S70.98021.18231.08011.03771.24321.13941.04161.17661.10211.36781.45101.38061.23501.24991.2411
S81.16001.47861.29131.13841.43301.27081.09941.16361.09961.47101.59191.49291.29521.39001.3024
S91.41581.64561.57281.36431.58451.52381.20701.29691.29301.65251.64541.66241.30991.41691.4251
S101.25601.22791.07951.20651.16831.03291.08101.10490.97311.49621.46771.42371.33861.29711.2941
S111.19791.31431.56681.13951.22761.40401.03661.12691.27921.45101.50781.58931.29001.34051.3882
S122.88352.88423.07102.89042.90743.12742.59932.56492.77672.41652.40342.45532.10372.00732.0381The south of Urumqi
S132.53362.17032.26602.44062.11242.19792.22321.90142.05912.28732.16232.12731.93081.75531.6863
S141.10832.39711.80651.21522.41631.87831.18702.13301.66891.35541.98191.67411.25121.59871.4626
S151.41641.80391.19161.47211.84531.22871.37941.64261.17851.54431.83031.45041.34031.56311.3092
S161.20251.34461.28951.14201.12001.20781.04871.15301.09501.48351.55651.53331.29941.34721.3399
S171.13421.07901.09051.13121.12571.13091.13821.09841.12831.48981.42821.43351.31941.26441.2813Fukang
S181.25721.26721.34091.22401.23571.30331.11851.11961.18921.53771.54961.53261.35561.36451.3788
S191.34341.24951.20231.17311.16751.13191.12971.04401.05791.63661.53781.47801.40371.33631.2958
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Zhu, J.; Duo, J.; Zhang, Z.; Pei, L.; Li, W.; Wufuer, R. Spectral Characteristics of Dissolved Organic Matter in Farmland Soils around Urumqi, China. Toxics 2023, 11, 376. https://doi.org/10.3390/toxics11040376

AMA Style

Zhu J, Duo J, Zhang Z, Pei L, Li W, Wufuer R. Spectral Characteristics of Dissolved Organic Matter in Farmland Soils around Urumqi, China. Toxics. 2023; 11(4):376. https://doi.org/10.3390/toxics11040376

Chicago/Turabian Style

Zhu, Jianhua, Jia Duo, Zizhao Zhang, Liang Pei, Wenfeng Li, and Rehemanjiang Wufuer. 2023. "Spectral Characteristics of Dissolved Organic Matter in Farmland Soils around Urumqi, China" Toxics 11, no. 4: 376. https://doi.org/10.3390/toxics11040376

APA Style

Zhu, J., Duo, J., Zhang, Z., Pei, L., Li, W., & Wufuer, R. (2023). Spectral Characteristics of Dissolved Organic Matter in Farmland Soils around Urumqi, China. Toxics, 11(4), 376. https://doi.org/10.3390/toxics11040376

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