Dissolved Organic Matter Quality Research Articles

Interactions between dissolved organic matter with different molecular weights and nonylphenol in surface water bodies

Dissolved organic matter (DOM) has a complex composition, which can interact with various pollutants and affect the removal of pollutants. Therefore, a thorough understanding of the interaction between the encccvironmental hormone nonylphenol (NP) and DOM is crucial for environmental impact and development. In this study, the interaction was investigated by means of excitation emission matrix (EEM) fluorescence spectroscopy, UV–Vis spectroscopy, FT-IR spectroscopy, nuclear magnetic resonance (NMR) and complex model analysis. The interaction between different MW DOM and NP was verified by the spectral characterization data. According to the characterization analysis, the main components of DOM in water samples were proteinoid (C1, C2, C4) with MW < 1 k Da, and their binding capacity (log Ka value) and binding site number (n) showed the maximum values (3.37, 3.24, 3.26; 0.81, 1.22, 0.52). For the humus like substance (C3) with larger molecular weight, the log Ka value and the number of binding points n increased with increasing molecular weight, and the maximum values were 3.13 and 0.31, respectively. It can be seen that low molecular weight proteins have strong binding ability and binding sites with NP, and high molecular weight humus also have strong binding ability. Overall, the interaction between DOM and NP has molecular weight dependence and heterogeneity. The purpose of this study is to deeply understand the interaction characteristics of different MW DOM with NP, and to provide theoretical support and reference for the study of the removal effects of NP pollutants.

Characterization of natural and anthropogenic dissolved organic matter in the yangtze river basin using FT-ICR MS

Dissolved organic matter (DOM) is a complex mixture that plays a crucial role in global carbon cycling and climate dynamics. Understanding the chemical composition of DOM is crucial for studying its biogeochemical behavior. However, identifying individual DOM molecules is challenging. Here, using ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry and an in-house database, we developed a framework to investigate DOM characteristics in natural water. Through the developed approach, we successfully identified thousands of individual DOM molecules in the water bodies of the Yangtze River Basin. For the first time, the proportions of natural and anthropogenic organics within DOM were revealed. In total, 9006 unambiguous molecular formulas were assigned to DOM in the Yangtze River Basin. The proportions of CHNO and CHOS compounds increased from upstream to downstream regions. Moreover, 1099 DOM compounds were tentatively identified, with 85 % being endogenous organics and 15 % being exogenous organics. Notably, lipids and pharmaceuticals and personal care products were the most frequently detected endogenous and exogenous compounds. The spatial variation of the identified DOM indicated anthropogenic discharges considerably increased both the number and abundance of DOM in the downstream Yangtze River Basin. This study highlighted the importance of anthropogenic impacts on DOM in water.

Molecular properties of dissolved organic matter leached from microplastics during photoaging process

The occurrence of dissolved organic matter (DOM) derived from microplastics (MPs) and its effect on aquatic systems has attracted great interest recently. However, the photoaging effect on the molecular structure of MP-derived DOM (MP-DOM) remains unclear. This paper presents the characteristics of DOM leached from three commercial MPs, i.e., polyethylene (PE), polypropylene (PP) and polyethylene terephthalate (PET) under UV irradiation. With prolonged aging periods, the surface roughness and oxygen-containing groups on the surface of MPs increase as more DOM leachate is generated. Moreover, the dissolved organic carbon (DOC) content of the leached DOM from PET MPs varies from 0.52 mg/L to 2.25 mg/L, which is higher than PE and PP MPs, due to the larger increased surface reaction area and the cleavage of the benzene ring. According to the excitation-emission matrix and parallel factor analysis (EEM-PARAFAC), the plastic-derived protein/phenolic-like components (C1 and C3) in MP-DOM were changed into photo-induced humic-like components (C2), which were closely related to the intermediates during photo-oxidation. High-performance liquid chromatography-mass spectrometry (HPLC−MS) analysis further identified that the highest proportion of antioxidants (24.8 %∼34.6 %) was contained in MP-DOM. Plasticizers, intermediate additives, and antimicrobial agents were also detected in DOM leachate. Correlation analysis identified that the composition of leached DOM was positively correlated with the surface roughness, the carbonyl index (CI), and the chemical groups of MPs. Moreover, a partial least square structural equation model (PLS−SEM) analysis further verified that the change of morphology and the chemical structure of MPs could affect the DOM structures and fractions directly. This study provides an in-depth understanding of the composition of MP-derived DOM during the aging process, as well as a comprehensive environmental impact assessment of MPs.

Applying fluorescence and 2D-correlation spectroscopy to elucidate changes in the chemical composition of DOM from soils with different vegetation types

ABSTRACT To understand the decomposition of the dissolved organic matter (DOM), four different soils (from grassland, spruce forest, oak forest, and agricultural land) were incubated at 15 °C, and the DOM changes were monitored using UV-Vis, synchronized fluorescence and 2D-correlation spectroscopy. The DOM fraction of the agricultural and grassland soils showed a significant increase in both SUVA values in the middle of the incubation ranging from an initial 3–5 L mg−1 m−1 to 40–50 L mg−1 m−1. Synchronous fluorescence spectroscopy revealed that at the beginning of incubation, on day 3, there was an increase in the proportion of low molecular-weight, readily biodegradable compounds (PLF, protein-like fluorescence), while from day 8 onwards, microbial degradation generated a large number of medium-molecular-weight molecules (MHLF, microbial humus-like fluorescence). At further sampling dates, the proportion of compounds of microbial origin decreased systematically, due to a decrease in microbial activity caused by the lack of substrate. 2D-correlation measurements revealed further details of the changes in the quality of DOM, revealing two distinct patterns in the DOM dynamics of the soils, the sequence MHLF→PLF being observed for grassland and arable land and PLF→HLF for forest soils, probably due to the different N supplies of the soils.

The Influence of Pyrolysis Temperature and Feedstocks on the Characteristics of Biochar-Derived Dissolved Organic Matter: A Systematic Assessment

Biochar is a carbon-rich product obtained by pyrolyzing biomass under oxygen-limited conditions and has a wide range of potential for environmental applications. In particular, dissolved organic matter (DOM) released from biochar has an important impact on the fate of pollutants. The study aimed to systematically assess how varying pyrolysis temperatures and biomass feedstocks influence the characteristics of biochar-derived DOM. DOM samples were comprehensively characterized utilizing UV-vis spectroscopy and excitation–emission matrix (EEM) fluorescence spectroscopy, coupled with parallel factor (PARAFAC) analysis. The study discovered that pyrolysis temperature significantly affects DOM characteristics more than feedstock type. An increase in pyrolysis temperature correlated with a notable decrease in dissolved organic carbon content, aromaticity, and fluorescence intensity, alongside a marked increase in pH and hydrophilicity. PARAFAC analysis identified three distinct DOM components: two humic-like substances (C1 and C2) and one protein-like substance (C3). The proportion of protein-like substances increased with higher pyrolysis temperatures, while the humic-like substances’ proportion declined. The compositional shifts in DOM with pyrolysis temperature may significantly influence its environmental behavior and functionality. Further research is necessary to explore the long-term environmental impact and potential applications of biochar-derived DOM.

Elucidating the Composition and Transformation of Dissolved Organic Matter at the Sediment-Water Interface Using High-Resolution Mass Spectrometry.

The exchange and transformation of dissolved organic matter (DOM) at the sediment-water interface are crucial factors in regulating watershed biogeochemistry, with the molecular composition of DOM serving as a pivotal determinant in elucidating this process. High-resolution mass spectrometry (HRMS) is an effective tool for resolving the composition of DOM. By analyzing the compositional characteristics of DOM at the sediment-water interface under three different salinities at the same latitude region in northern China, the findings indicate certain variations in component characteristics of DOM between low-salinity inland waters and high-salinity seawaters, with the former exhibiting greater molecular diversity and higher molecular weights, whereas the latter displayed a higher saturation and bioavailability. Notably, the presence of more CHOS substances in the low-salinity inland waters underscores the transformation of the DOM influenced by terrestrial inputs and anthropogenic activities. Conversely, the presence of more CHO and CHNO substances in high-salinity seawater underscores the microbial effects. The chemical transformation process from overlying water to pore water to sediments was characterized by methylation, hydrogenation, decarboxylation, and reduction, as determined by calculating the relations between the H/C and O/C ratios of different compound types. These findings indicate that HRMS can yield more refined results in revealing the process of DOM at the sediment-water interface under different environments, which provides a more reliable basis for a deeper understanding of the source-sink mechanism of sediment organic matter.

Qualitative variability of dissolved organic matter in the Baltic Sea sediments apparent from fluxes and optical properties

IntroductionThe release of dissolved organic matter (DOM) from sediments serves as an important part of the carbon cycle.MethodsHere, we address pore water DOM quality and its release from shallow sediments (0–10 cm) of the central and southern Baltic Sea - Gdansk, Bornholm, and Eastern Gotland Basins - using excitation–emission matrix spectroscopy and size-exclusion chromatography.ResultsDOM release from sediments displayed spatial variability, with diffusive DOC fluxes ranging from 0.02 to 1.06 mmol m−2 d−1, and basin-averaged fluxes increased in the order Gotland &amp;lt; Bornholm &amp;lt; Gdansk. DOM qualitative characteristics also varied among investigated basins. In the oxygen-limited study sites from the Gdansk Basin, we observed elevated abundances of low apparent molecular weight DOM fraction and proteinaceous-like fluorescent DOM, while in the Bornholm Basin, pore water DOM was generally more humic-like and of higher apparent molecular weight. Pore waters from the deepest study sites in the Gotland Basin were qualitatively very similar to those of the pore waters from the upper sediment layers (0–4 cm) from all other investigated sites, suggesting little organic matter reworking at depth at those stations.DiscussionOur results suggest that the spatial variability in the magnitude of DOM release may be linked to the qualitative differences of DOM in sediments.

Molecular–level insights into the synergistic activation of peracetic acid by ultraviolet and ferrous ions for the degradation of sedimentation sludge water in drinking water treatment plants based on Fourier transform-ion cyclotron resonance mass spectrometry

Sedimentation sludge water (SSW) from sedimentation tanks in drinking water treatment plants contains significant amounts of dissolved organic matter (DOM) and precursors of disinfection byproducts, raising increasing concerns about the safety of finished water following SSW recycling. This study explores the alterations in bulk properties and molecular characteristics of DOM in SSW treated with ultraviolet (UV)/ferrous ions (Fe2+) and peracetic acid (PAA) using fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT–ICR MS). The primary reactive species, hydroxyl radicals (·OH) and acylperoxy radicals (CH3C(O)OO·) achieved degradation rates of up to 82.0%, eliminating 84.5% of total fluorescent components and reducing molecular intensity and apparent molecular count by 90.9% and 69.8%, respectively. This treatment significantly reduced the aromaticity of DOM, leading to the formation of more oxidized and stable compounds. Reaction mechanisms indicate that ·OH and CH3C(O)OO· primarily facilitate oxygen addition and dehydrogenation, while CH3C(O)OO· promotes decarboxylation through weak electron transfer processes. The treatment preferentially removes complex DOM containing nitrogen and sulfur heteroatoms, which are key precursors of disinfection byproducts. These findings enhance our understanding of DOM transformations during UV/Fe2+/PAA treatment and provide valuable insights into the safe recycling of SSW.

Characteristics of Dissolved Organic Matter as Affected by Decomposition of Different Organic Materials in Alpine Wetland

Dissolved organic matter (DOM) plays a significant role in the nutrient supply, energy flow, and pollutant transportation in the wetland ecosystem. However, little is known about the effect of the decomposition of different organic materials in alpine wetland water on the DOM characteristics. By conducting a 90-day decomposition experiment with the addition of different organic materials (peat soil, yak manure, and plant litter) alone or their combinations into alpine wetland water, we characterized the water DOM using three-dimension excitation-emission matrix spectroscopy. The results showed that the decomposition of organic materials significantly affected the chemical properties, sources, humification degree, and composition of the water DOM. The decomposition increased dissolved organic carbon and dissolved total nitrogen in the water. For most of the water samples, a fluorescence index ranging from 1.4 to 1.7 and a biological index of less than 0.8 may indicate that both autochthonous and allochthonous sources contributed to the water DOM, which may primarily rely on allochthonous sources. UVA (37.55–46.81% of total fluorescent components) and UVC fulvic-like substances (29.91–35.53% of total fluorescent components) dominated the water DOM compositions. Among the treatments, additions of peat soil and yak manure led to the highest and the lowest humification degree of the water DOM, respectively. For the treatment of the combination decomposition of all three organic materials, the yak manure may stimulate microbial activity and facilitate the decomposition of plant litter and peat soil and, therefore, boost the humic-like substances in the water DOM. These findings may help the development of wetland biomass management with the objective of maintaining alpine wetland ecosystem services.

Influences of wildfire on the soil dissolved organic matter characteristics and its electron-donating capacity

Global increases in the intensity and frequency of wildfires are driving major changes in soil organic matter (SOM) characteristics, including soil dissolved organic matter (DOM). As the most crucial component of SOM, soil DOM plays a pivotal role in the carbon cycle and regulates the environmental fate of contaminants through its versatile reactivities, including electron-donating capacity (EDC). However, it is still being determined how wildfire influences key characteristics of soil DOM and subsequent effects on EDC in forest soils. Thus, we conducted our study to fill this gap with the forest soils of Jinyun Mountain Nature Reserve of China, which experienced an unprecedented wildfire event in 2022. The results from optical characterization, high-performance size-exclusion chromatography (HPSEC), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) showed decreasing molecular weight but elevating nitrogen-containing molecular formulas of soil DOM in the burned soils. This could be attributed to the Maillard reaction and microbial re-colonies. Additionally, wildfires increased the condensed aromatics and lignin components in soil DOM. In the burned soils, we observed increasing EDC of soil DOM, which accounts for an increase in lignin-derived phenolic components. Overall, the findings of this study demonstrate that eco-disturbances, such as wildfires, induce alterations in the properties of DOM, leading to variations in its reactivity and potentially influencing the fate of environmental pollutants beyond carbon dynamics alone. Thus, incorporating the dynamic properties of soil DOM, particularly in the context of climate change, can enhance the assessment of risks associated with contaminants in soil and water, providing valuable insights.

Seasonal changes of dissolved CO2 and its linkage with optical characteristics of DOM in groundwater in agricultural areas

Groundwater contains significant quantities of dissolved CO2, which are crucial contributors to the global carbon cycle. Dissolved organic matter (DOM) functions as a principal carbon and energy source for microbial communities within groundwater ecosystems, yet the relationship between dissolved CO2 and optical characteristics of DOM remains ambiguous. Here, we delineate the variations in seasonal and vertical distribution of dissolved CO2 concentrations and DOM optical characteristics, and assess their interconnections in the groundwater of an agricultural region. The results showed that the average concentration of dissolved CO2 in groundwater was 11,300 ± 5,788 ppm, with the highest levels observed in summer and the lowest in winter. Additionally, shallow wells exhibited higher concentrations of dissolved CO2 compared to deep wells. The mass balance calculation suggested that 40,092 t of CO2 are released annually due to the degassing of supersaturated CO2 from groundwater extraction. Three-dimensional fluorescence with parallel factor analysis (EEM-PARAFAC) identified five components of DOM in groundwater: Components C1, C2, C3 and C4 are humic-like substances, and C5 is a tryptophan-like substance associated with protein structures. The analysis of compositional features and fluorescence indices revealed that DOM is predominantly derived from microbial sources, with mixed contributions from terrestrial sources in groundwater. Principal component analysis (PCA) showed that first two axes accounted for 74.7 % of the variance in the seasonal variation of DOM optical characteristics and dissolved CO2 concentration, which reveals that DOM decomposition contributes to CO2 saturation in groundwater. However, a larger proportion of CO2 may be derived from leaching in the vadose zone during the rainy season or irrigation periods in shallow aquifer. This study enhanced the understanding of carbon dynamics within agricultural groundwater.

Exploring the variations in molecular characteristics of dissolved organic matter driven by aquaculture types

In recent decades, global aquaculture has expanded rapidly, raising concerns about coastal environmental degradation due to unregulated or poorly regulated discharge of aquaculture tailwater. Despite the crucial role of dissolved organic matter (DOM) in biogeochemical processes and aquatic biodiversity, the influence of aquaculture type on the molecular characteristics of DOM remains largely unexplored. Herein, this study investigated the variations in chemical and spectroscopic properties as well as molecular characteristics and composition of DOM across different aquaculture types including crustacean, fish and shellfish. Our findings revealed notable differences in DOM quantities among different aquaculture types, with crustacean and fish aquaculture water containing higher DOM amount compared to shellfish aquaculture water. This disparity can be attributed to the more frequent formulated feeds of crustacean and fish in contrast to shellfish aquaculture. Furthermore, distinct differences were also observed in the characteristics and composition of DOM among the different aquaculture waters. Specifically, DOM in shellfish aquaculture water exhibited a higher abundance of unsaturated and reduced molecules as well as increased aromaticity compared to the other two aquaculture waters. Conversely, DOM from fish aquaculture water showed a greater contribution from terrestrial origin characterized by elevated levels of plant-based components such as lignin-like and tannin-like compounds. Interestingly, DOM from shellfish aquaculture water contained lower levels of microbial-derived components such as lipid-like and protein-like compounds, likely due to reduced microorganism populations resulting from lower nutrients availability and higher salinity. Overall, these significant variations in characteristics and composition of DOM underscore the potential impacts of aquaculture type on the DOM biogeochemical cycle and the environmental quality in aquatic ecosystems.

Effects of mineral adsorption on the molecular composition of soil dissolved organic matter: Evidence from spectral analyses

The adsorption of soil dissolved organic matter (DOM) by minerals is crucial for long-term carbon storage and has been extensively studied. However, the variations in soil DOM composition resulting from adsorption by different minerals have rarely been investigated from a spectral perspective. This study examined the impact of non‑iron (kaolinite) and iron-bearing (ferrihydrite) minerals on the concentration and characteristics of DOM from dark brown soil during a 60-h-long incubation experiment. Soil dissolved organic carbon was removed more efficiently by ferrihydrite (66.2 %) than by kaolinite (14.8 %). UV–Vis spectroscopic analysis indicated that DOM with high aromaticity and molecular weight exhibited a strong affinity for both ferrihydrite and kaolinite. The fluorescence of soil DOM decreased in the ferrihydrite treatment, with a notable reduction in humic-like fluorescent components identified through fluorescent excitation-emission matrix coupled parallel factor analysis. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy revealed that carboxyl groups were critical in DOM adsorption on ferrihydrite, participating in ligand exchange, hydrogen bonding, and electrostatic attraction. This study highlights the important role of iron-bearing minerals in soil carbon sequestration and demonstrates how different mineral alter soil DOM composition, potentially influencing the cycling of organic carbon in terrestrial systems.

Land Use Cover and Flow Condition Affect the Spatial Distribution Characteristics of Fluorescent Dissolved Organic Matter in the Yongding River

Dissolved organic matter (DOM) is involved in many biogeochemical processes and plays an important role in aquatic ecosystems. This study integrated three-dimensional fluorescence excitation–emission matrix (EEM), fluorescence regional integration (FRI), and parallel factor analysis (PARAFAC) to better understand the distribution and component characteristics of DOM in the Yongding River and explore the response of DOM to natural and anthropogenic activities. The results showed that the relative abundance of fulvic-like materials of DOM in the river was the highest, with an average of 68.64%. PARAFAC identified three fluorescent components, namely, C1 (microbial humic-like components), C2 (terrestrial humic-like components), and C3 (protein-like components), and their changes with flow confirmed that the riverine DOM was generally influenced by microbial sources and terrestrial inputs. The upper reaches showed strong autochthonous characteristics and a high humification degree of DOM due to a fast flow rate, while the middle reaches showed biological or aquatic bacterial origin due to a moderate flow rate. The lower reaches of the river showed characteristics of biological and bacterial origin, most strongly influenced by human activities. The findings can help provide a basis for identifying DOM characteristics in the Yongding River basin and understanding the geochemical cycle of DOM at a regional scale.

Unraveling the role of anthropogenic and hydrologic drivers with respect to the optical and molecular properties of dissolved organic matter and organic phosphorus in a P-contaminated river

Anthropogenic and hydrological drivers are key factors influencing the fate of dissolved organic matter (DOM) and dissolved organic phosphorus (DOP) in river runoff. However, how anthropogenic disturbances and hydrological conditions jointly affect the composition and characteristics of DOM and DOP in river runoff remains unclear. This study used fluorescence spectroscopy, Fourier transform ion cyclotron resonance mass spectrometry, and the stable water isotopes to interpret the chemical composition and properties of DOM and DOP as well as their linkages to anthropogenic disturbances and hydrological conditions in a typical P-contaminated tributary to the central Yangtze River. The results show in the wet season, the average abundance of humic-like components in DOM exceeded 60 %, while the average abundance of tryptophan-like components in DOM exceeded 50 % in the dry season. During the dry season, hydrological conditions had a greater impact on highly unsaturated DOM compounds compared to anthropogenic disturbances because a decrease in precipitation reduced the transport of terrestrial DOM into aquatic systems and increased water retention time in the river, promoting the production of unsaturated compounds from photochemistry. The effects of the two factors were similar in the wet season because active agricultural activities and intense precipitation jointly facilitated the entry of exogenous humics into the runoff, leading to the similar relative abundance of highly unsaturated DOM compounds associated with both factors. Anthropogenic disturbances had a greater impact on aliphatic DOM and DOP than hydrological conditions, which was associated with intense human activities in the watershed, such as phosphate mining, agricultural cultivation, and domestic sewage discharge. This study provides new knowledge about the composition, properties and underlying mechanisms of DOM and DOP in the P-contaminated watershed runoff.

Microplastics and benthic animals reshape the geochemical characteristics of dissolved organic matter by inducing changes in keystone microbes in riparian sediments

Dissolved organic matter (DOM) in riparian sediments plays a vital role in regulating element cycling and pollutant behavior of river ecosystems. Microplastics (MPs) and benthic animals (BAs) have been frequently detected in riparian sediments, influencing the substance transformation in river ecosystems. However, there is still a lack of systematic investigation on the effects of MPs and BAs on sediment DOM. This study investigated the impact of MPs and BAs on the geochemical characteristics of DOM in riparian sediments and their microbial mechanisms. The results showed that MPs and BAs increased sediment DOC concentration by 34.24%∼232.97% and promoted the conversion of macromolecular components to small molecular components, thereby reducing the humification degree of DOM. Mathematical model verified that the changes of keystone microbes composition in sediments were direct factors affecting the characteristics of DOM in riparian sediment. Especially, MPs tolerant microbes, including Planctomicrobium, Rhodobacter, Hirschia and Lautropia, significantly increased DOC concentration and decreased humification degree (P < 0.05). In addition, MPs and BAs could also influence keystone microbes in sediments by altering the structure of microbial network, thereby indirectly affecting DOM characteristics. The study demonstrates the pollution behavior of MPs in river ecosystems and provides a basis for protecting the ecological function of riparian sediments from MPs pollution.

Spectral Characteristics of Dissolved Organic Matter in Sediments from Yuanhe River Basin

Dissolved organic matter （DOM） plays an important role in indicating the pollution of the water environment, and sediment is the main source of endogenous pollution of the water environment. Research on the spectral characteristics of DOM in sediments was important for the interpretation of water environment pollution. In this study, UV-visible absorption spectroscopy and three-dimensional fluorescence spectroscopy combined with the parallel factor analysis （PARAFAC） were used to analyze the fluorescent components, sources, and influencing factors of DOM in sediments from the Yuanhe River Basin. The results showed that the average of ω（TN）, ω（TP）, and ω（OM） in sediments from the Yuanhe River Basin were 0.52, 0.66, and 21.22 g·kg-1, respectively. The concentrations of total nitrogen and total phosphorus increased along the flow direction. In addition, the sediment DOM from the Yuanhe River Basin mainly originated from terrestrial sources. The chromophoric DOM concentration and aromaticity of DOM from the downstream reaches were significantly higher than those from the upstream and midstream reaches. Based on PARAFAC, four fluorescent components of DOM in sediments from the Yuanhe River Basin were identified, including three humus-like components （C1, C3, and C4） and one protein-like component （C2）. The sediment DOM was dominated by humus-like materials. Moreover, the fluorescent intensity of the fluorescent components was higher in the downstream reaches. Redundancy analysis revealed that the physicochemical properties of sediments in the mainstream and downstream reaches played a more significant role in the spectral properties of DOM. Phosphorus pollution and the terrestrial humus-like substance of sediment DOM were homologous. These results indicated that the spectral properties of DOM were the indicator of water environmental pollution in the region with strong anthropogenic influence.

Revealing degradation pathways of soluble and dissolved organic matter in alluvial-lacustrine aquifer systems impacted by high levels of geogenic ammonium

The excessive presence of geogenic ammonium (NH4+) in groundwater poses a global environmental concern, commonly linked to the degradation of nitrogen-containing dissolved organic matter (DOM). However, there is a gap in systematic studies on the combination of soluble organic matter (SOM) in sediments and DOM in groundwater, with few indoor incubation experiments to validate their degradation pathways. This study utilized ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry to analyze the molecular characteristics of DOM and SOM in aquifer systems affected by geogenic NH4+. Subsequently, indoor incubation experiments spanning up to 140 d were conducted to verify the degradation pathways. The experimental results revealed a two-phase degradation process for both the DOM and SOM. The initial stage was characterized by the degradation of aliphatic compounds (ALC) with the production of polyphenols (PPE) and highly unsaturated compounds (HUC). The second stage was dominated by the degradation of PPE and HUC, accompanied by the re-consumption of some ALC, while more recalcitrant HUC persisted. Notably, the first stage of SOM degradation exceeded that of DOM degradation, indicating that SOM exhibited greater resistance to aging. This phenomenon may be attributed to a wider range of active enzymes in sediments, the rapid replenishment of SOM by organic matter in sediments, or the accelerated degradation of DOM. The experimental results aligned with the molecular characterization of DOM and SOM in actual aquifer systems. It is hypothesized that NH4+ produced through the direct mineralization of SOM may contribute more to the enrichment of NH4+ in groundwater than that produced through the mineralization of DOM. This study is the first to analyze DOM and SOM together in aquifer systems and validate their degradation pathways through incubation experiments, thereby providing novel insights into the enrichment of geogenic NH4+ in groundwater.

Spatiotemporal response of the optical characteristics of dissolved organic matter to seasonality and land use in tropical island rivers.

Dissolved organic matter (DOM), a pivotal component in the global carbon cycle, plays a crucial role in maintaining the productivity and functionality of aquatic ecosystems. However, the driving factors of variations in the properties of riverine DOM in tropical islands still remain unclear. In this study, the spatiotemporal response of the optical characteristics of riverine DOM to seasonality and land use on Hainan Island in southern China was investigated. Our results revealed that DOM in the rivers of Hainan Island exhibited a relatively high proportion of fulvic acid and demonstrated strong terrestrial sources. The optical properties of DOM exhibited significant variations both seasonally and spatially. Land use exerted a dominant influence on riverine DOM. Specifically, during the wet season, riverine DOM exhibited larger molecular weight, increased chromophoric DOM (CDOM) abundance, and higher Fmax compared to the dry season. Furthermore, riverine DOM influenced by grassland and farmland showed higher CDOM abundance, Fmax, and humification degree in contrast to those impacted by forest and urban. Random forest and correlation analysis results indicated that grassland and farmland enhanced the Fmax of DOM by increasing levels of TP, NO3--N, Chl a, and NH4+-N in the dry season. However, during the wet season, the increased Fmax of DOM induced by grassland and farmland relied on the increments of Chl a and TP concentrations. This study improves our understanding of the spatiotemporal fluctuations of DOM in the rivers of Hainan Island, highlighting the effects of season and land use on DOM. It offers valuable support for improving water quality and contributes to enhancing human comprehension of the global carbon cycle.

Temporal Variations in Fire Impacts on Characteristics and Composition of Soil-Derived Dissolved Organic Matter at Qipan Mountain, China.

Dissolved organic matter (DOM), the most reactive fraction of forest soil organic matter, is increasingly impacted by wildfires worldwide. However, few studies have quantified the temporal changes in soil DOM quantity and quality after fire. Here, soil samples were collected after the Qipan Mountain Fire (3-36 months) from pairs of burned and unburned sites. DOM contents and characteristics were analyzed using carbon quantification and various spectroscopic and spectrometric techniques. Compared with the unburned sites, burned sites showed higher contents of bulk DOM and most DOM components 3 months after the fire but lower contents of them 6-36 months after the fire. During the sharp drop of DOM from 3 to 6 months after the fire, carboxyl-rich alicyclic molecule-like and highly unsaturated compounds had greater losses than condensed aromatics. Notably, the burned sites had consistently higher abundances of oxygen-poor dissolved black nitrogen and fluorescent DOM 3-36 months after the fire, particularly the abundance of pyrogenic C2 (excitation/emission maxima of <250/∼400 nm) that increased by 150% before gradually declining. This study advances the understanding of temporal variations in the effects of fire on different soil DOM components, which is crucial for future postfire environmental management.