Insight into the dynamics of dissolved organic matter components under latitude change perturbation.

Dissolved organic matter (DOM) which can help the transportation of nutrients and pollutants plays essential role in the aquatic ecosystems. However, the dynamics of individual DOM component under the change of latitude have not been elucidated to date. The composition and dynamics of DOM were assessed in this study. Two individual parallel factor analysis (PARAFAC) components were found in each sampling site in Heilongjiang. To further characterize the inner change of the identified PARAFAC components, two-latitude correlation spectroscopy (2DCOS) technique was applied to the excitation loadings data. Interestingly, not all the fluorophore in a PARAFAC component change in the same direction as the overall change of a component. From upstream to downstream, the peak A1 in PARAFAC component C1 showed a downward trend, but peak A2 presented an upward trend. In PARAFAC component C2, the peak T2 and peak T3 showed an inverse changing trend under latitude perturbation. Furthermore, basic nutrients parameters in Heilongjiang were also characterized in each sampling sites. The relationships between DOM and nutrients showed that component C1 made a significant contribution to chemical oxygen demand (COD) and biochemical oxygen demand (BOD5). The evolutions of DOM peak A1 and peak A2 were accompanied by the changing of Total phosphorus (TP). The findings in this study could make a contribution to explore the fate of DOM in high humic-like substance containing river.

The driving mechanism of diverse land use types on dissolved organic matter characteristics of typical urban streams from Wuhan city.

Urban streams play a crucial role in water network connectivity, drainage and urban landscaping, and receive abundant allochthonous dissolved organic matter (DOM), which is derived from nature and human activities. However, the influence of diverse land use types on the spatiotemporal distribution and characteristics of DOM in typical urban streams is still not fully understood. Therefore, the water sample collection and data analysis campaign were carried out in Wuhan in summer and winter. By using parallel factor analysis (PARAFAC) model, two humic-like substances and one protein-like component were eventually identified, and the specific DOM charcteristics of urban streams in industrial area illustrated the impact of allochthonous DOM caused by anthropogenic activities on their properties. The characteristics of DOM presents spatiotemporal distribution differences, and the fluorescence intensity of DOM in summer was significantly higher than that in winter, mainly due to the variation of allochthonous input from precipitation and runoff. Significant differences of the DOM concentration and composition in urban streams under different vegetation coverage were found, indicating that extreme human disturbance and high vegetation coverage can both greatly change DOM characteristics in urban streams. Redundancy analysis (RDA) revealed an indirect driving effect of land use on DOM, and the influence was considerably stronger in summer. The partial least squares structural equation modelling (PLS-SEM) analysis showed that land use can directly affect DOM content of urban streams (-0.147), with anthropogenic land use playing a positive role and natural land use the reverse, and indirectly change DOM concentration by influencing DOM origin (0.128), nutrients (0.022) and heavy metals (0.021). Moreover, human social and economic structure in anthropogenic land use can affect DOM components and sources of urban streams. This study revealed the driving mechanism of land use impact on DOM characteristics and improve our understanding of DOM geochemical cycling in urban streams.

Persistence of dissolved organic matter in sediments influenced by environmental factors：Implication for nutrition and carbon cycle.

The persistence of dissolved organic matter (DOM) plays a crucial role in the cycling and distribution of carbon and nutrients. Nonetheless, our understanding of how environmental alterations affect the persistence of sedimentary DOM remains incomplete. Excitation Emission Fluorescence Matrix-Parallel Factor Analysis (EEM-PARAFAC) was used to examine the fluorescence and compositional characteristics of hydrophilic and hydrophobic DOM (separated using XAD-8 resin) within sediments from twelve lakes and reservoirs. Fluorescence analysis indicated that DOM persistence is dependent on the proportions of the three components derived from PARAFAC. The Mantel test showed that climatic factors had the most significant impact on DOM persistence (Mantel's r = 0.46-0.54, Mantel's p = 0.001-0.007), while anthropogenic (Mantel's r = 0.24-0.32, Mantel's p = 0.03-0.05) and hydrological factors (Mantel's r = 0.03-0.22, Mantel's p = 0.06-0.40) had a somewhat lesser influence. Environmental changes resulted in a consistent decline in DOM persistence from Northeast to Southwest China, accompanied by an increase in gross primary productivity (GPP). Reduced DOM persistence due to climate, hydrological, and anthropogenic factors may lead to elevated concentrations of total phosphorus (TP), contributing to deteriorating water quality and events such as algal blooms. The decline in water quality due to reduced DOM persistence in lakes with high GPP can exacerbate the transition from carbon sinks to carbon sources. Consequently, the persistence of sedimentary DOM significantly influences nutrient and carbon cycling in lakes. Investigating DOM persistence in lakes across diverse geographic locations offers a new perspective on lake eutrophication and carbon emissions. Furthermore, it is crucial to develop targeted recommendations for lake restoration and management.

The priming effects of plant leachates on dissolved organic matter degradation in water depend on leachate type and water stability.

The modification of dissolved organic matter (DOM) degradation by plant carbon inputs represents a critical biogeochemical process that controls carbon dynamics. However, the priming effects (PEs) different plant tissues induce on the degradation of DOM pools with different stabilities remain unknown. In this study, PEs, induced by different tissue leachates of Phragmites australis, were evaluated via changes in DOM components and properties of both fresh and tidal water (with different stabilities). The results showed that DOM derived from different plant tissue leachates differed in composition and bioavailability. Inputs of tissue leachates induced PEs with different intensities and directions (negative or positive) on DOM degradation of fresh and tidal water. In fresh water, the PEs of leaf and root leachates were significantly higher than those of stem and rhizome leachates. The PE direction changed for DOM degradation between fresh and tidal water. The addition of leaf and root leachates tended to induce positive PEs on DOM degradation of fresh water, while resulting in negative PEs on DOM degradation of tidal water. Negative PEs for tidal water DOM may be due to preferential utilization of microbes, high salinity, and/or the promotion of exogenous DOM production from plant tissues. The results indicate that intensity and direction of PEs induced by plant leachates depend on both leachate type and water stability. The findings highlight the necessity to examine the nature of exogenous and native DOM when interpreting the interactive processes that regulate DOM degradation.

Sources, characteristics, and in situ degradation of dissolved organic matters: A case study of a drinking water reservoir located in a cold-temperate forest.

Dissolved organic matter (DOM) plays a pivotal role in the biogeochemical cycles of elements and the regulation of forest ecosystem functions. However, studies on the regional and seasonal characteristics of DOM in cold-temperate montane forests are still not comprehensive. In this study, samples of water, soil, and sediment from different sites in the forest drainage basin were collected, and their DOM was characterized by an excitation-emission matrix and parallel factor analysis (EEM-PARAFAC). The results showed that terrestrial-sourced humic-like substances were the dominant DOM in the studied reservoir and inflowing rivers. The quality and quantity of DOM exhibited spatiotemporal variations with the influence of terrain and monsoonal precipitation. The average concentration of dissolved organic carbon (DOC) in the wet season was 11.62 mg/L, which was higher than that in the dry season (8.18 mg/L). Higher humification index (HIX) values were observed in the wet season and upstream water than in the dry season and reservoir water. Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) was used to further develop a molecular-level understanding of the in situ degradation process of DOM. The results indicated that photodegradation rather than biodegradation may play a dominant role in the in situ degradation of terrestrial-sourced humic-like substances under natural conditions. The biodegradability of DOM was enhanced after the in situ degradation process. Additionally, a significant decrease in the precursors of disinfectant byproducts in DOM was observed after in situ degradation. To our knowledge, this is the first study of the sources, characteristics, and in situ degradation of DOM in a reservoir in a cold-temperate forest. These findings help better understand the quality, quantity, and biogeochemical process of DOM in the studied reservoir and may contribute to the selection of drinking water treatment technologies for water supply.

Insight into humification of mushroom residues under addition of Rich-N sources: Comparing key molecular evolution processes using EEM-PARAFAC and 2D-FTIR-COS analysis.

Accelerating the humification of organic solid waste is one of the most important issues in composting. This present study aims to study and compare the humification process of different rich-N sources (chicken manure, cattle manure, and urea) addition during the composting of mushroom residues, from macro physicochemical properties to micro humic molecular structure evolution process. The physicochemical elements and humic components were determined for evaluating the compost quality and humification degree as composting proceed. The coupled analysis of excitation-emission matrix with parallel factor analysis (EEM-PARAFAC) and two-dimensional correlation with Fourier transform infrared spectrum (2D-FTIR-COS) were used to characterize the functional molecular structure evolution of dissolved organic matter during humification process. The results indicated that the rank order for humification level were the treatments of chicken manure (HM), urea (UM), cattle manure (CM), and single mushroom residue treatment (CK), with their humification index of 22.18%, 22.05%, 18.47%, and 16.52%, respectively. Humic substance, humic acid, and fulvic acid were obtained the highest in HM treatment with contents of 35.41 ± 0.86%, 23.32 ± 1.57%, and 10.97 ± 0.52%, respectively. The rich-N source addition enhanced the degradation of protein-like and polysaccharides-like substances in dissolved organic matter, thus accelerating the humification process of mushroom residues. The key structure evolution of dissolved organic matter in the HM treatment, in which the CO and CC stretching of quinone, amide, or ketone, and the C-O stretching of polysaccharides may be responsible for the faster formation of humus compared to the other nitrogen treatments. In this study, redundancy analysis indicated that the total nitrogen (TN) and nitrate nitrogen (NO3--N) may be the potential indicators for determining the humification level as composting proceed. The result provides significant insight into the humification mechanism of mushroom residue under different types of nitrogen sources at the molecular level, and will be reference for improving the composting technique in practical field.

Insight into variation and controlling factors of dissolved organic matter between urban rivers undergoing different anthropogenic influences.

Dissolved organic matter (DOM), known as a key to the aquatic carbon cycle, is influenced by abiotic and biotic factors. However, the compositional variation and these factors' effects on fluorescence DOM (FDOM) in urban rivers undergoing different anthropogenic pressure are poorly investigated. Herein, using fluorescence excitation-emission matrix and parallel factor analysis (EEM-PARAFAC), four FDOM components (C1, C2, C3, and C4) were identified in a less urbanized north river (NR) and a more urbanized west river (WR) of Jiulong River Watershed in Fujian province, China. C1, C2, and C4 were related to humic-like substances (HLS) and C3 to protein-like substances (PLS). HLS (63.9% in WR and 36.4% in NR) and PLS (62.7% in WR and 37.3% in NR) exhibited higher fluorescence in the more urbanized river. We also found higher PLS in winter, but higher HLS in summer for both rivers. Although the coefficient of variation indicated a difference in FDOM components stability to some extent between the two rivers, the typhoon event that occurred in summer had a stronger disruptive impact on the CDOM and FDOM of a more urbanized river than that of a less urbanized river. We explore abiotic and biotic factors' effects on FDOM using the partial least squares path model (PLS-PM). PLS-PM results revealed higher significant influences of biotic factors on FDOM in the more urbanized river. This study enhances our understanding of FDOM dynamics of rivers with different anthropogenic pressure together with the abiotic and biotic factors driving them.

Biogeochemical processes controlling the dynamics of dissolved organic matter in streams in the Shirakami Mountains, Japan.

The Shirakami Mountain range, including the largest primeval beech forest in East-Asia, is undergoing ecological change. Dissolved organic matter (DOM) plays an important role in nutrient and material cycling in forest ecosystems. Because the quality of DOM varies based on its origin and diagenetic and runoff processes, changes in the environment surrounding DOM can be rapidly detected by monitoring its quality. Herein, concentrations and fluorescence composition of DOM at 14 sites in 13 streams in the Shirakami Mountain range were monitored monthly for over 2 years, excluding winter (December-March), to gain insight into the catchment hydrological and soil characteristics affecting DOM concentrations and composition in stream water. Based on the pattern of temporal changes in fluorescent component composition, monitoring sites were categorized into four groups (streams with small catchments, large catchments, catchments facing the Sea of Japan, and open waters in the catchment) with similar catchment characteristics affecting DOM dynamics. Multiple linear regression analysis showed that DOM concentrations in each group could be attributed to rainfall on the survey date, short-term (1-2 days) rainfall, midterm (~1 month) accumulated rainfall, midterm (7-11 days) accumulated temperature, and catchment characteristics as explanatory variables. The degree of influence of these variables differed among the four groups. The results of this study show that grouping streams according to catchment hydrological characteristics can help identify the impact of climate and environmental change on DOM dynamics in stream water.

Deciphering the Fingerprint of Dissolved Organic Matter in the Soil Amended with Biodegradable and Conventional Microplastics Based on Optical and Molecular Signatures.

Biodegradable polymers are promoted as promising alternatives for conventional non-degradable plastics, but they may also negatively impact soil ecosystems. Here, we estimated the effects of biodegradable (polylactide (PLA) and polybutylene succinate (PBS)) and non-biodegradable (polyethylene (PE) and polystyrene (PS)) microplastics at a concentration of 1% (w/w) on dissolved organic matter (DOM) in two soil types, a black soil (BS) and a yellow soil (YS), by using fluorescence excitation-emission matrix spectroscopy and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). PBS significantly increased the contents of soil dissolved organic carbon (DOC) and the relative intensities of protein-like components. The turnover rates of soil DOM were statistically higher in PBS treatments (0.106 and 0.196, p < 0.001) than those in other microplastic groups. The FT-ICR-MS results indicated that more labile-active DOM molecules were preferentially obtained in biodegradable microplastic treatments, which may be attributed to the polymer degradation. The conventional microplastics showed no significant effects on the optical characteristics but changed the molecular compositions of the soil DOM. More labile DOM molecules were observed in BS samples treated with PE compared to the control, while the conventional microplastics decreased the DOM lability in YS soil. The distinct priming effects of plastic-leached DOM may trigger the DOM changes in different soils. This study provided important information for further understanding the impact of microplastics on soil carbon processes.

The source apportionment of N and P pollution in the surface waters of lowland urban area based on EEM-PARAFAC and PCA-APCS-MLR.

Multiple sources contribute to nitrogen(N) and phosphorus (P) pollution in lowland urban rivers, and apportioning the sources of N and P pollution is essential for improving the ecological health of urban environments. Three urban polders in Jiaxing were selected to investigate the temporal variations of N and P pollutants in lowland urban river waters under dry and wet conditions. Moreover, the main potential sources of N and P pollution were identified through the correlations of pollutants and components of dissolved organic matter (DOM) derived from excitation-emission matrix (EEM) and parallel factor analysis (PARAFAC). The results indicate that the main pollution sources identified with PCA method were consistent with the potential sources revealed by DOM's EEM-PARAFAC components. Furthermore, absolute principal components score combined with multivariate linear regression (APCS-MLR) was conducted. The results illustrated that domestic wastewater contributes more than 70% of N pollution and river-bottom sediments contribute more than 50% of P pollution under dry conditions. On the contrary, discharged water from the stormwater outlets contributes more than 41% of P and 75% of N under wet conditions. Specifically, about 48% of them come from domestic wastewater, and about 38% come from urban surface runoff. This study highlights the effectiveness of DOM components derived from EEM-PARAFAC in identifying the sources of N and P pollution and the PCA-APCS-MLR in apportioning the contributions of each potential pollution source in lowland urban rivers.

Spectroscopic characterization of dissolved organic matter from macroalgae Ulva pertusa decomposition and its binding behaviors with Cu(II).

Dissolved organic matter (DOM) from macroalgae is regarded a crucial source of autochthonous DOM in coastal ocean. In the present study, the characteristics of DOM from the macroalgae Ulva pertusa decomposition (U. pertusa-DOM) and its binding behaviors with Cu(II) using multiple spectroscopic techniques and chemometric analyses. The labile U. pertusa-DOM could be consumed and transformed by microorganisms. The absorption spectroscopic descriptors indicate that the hydrophobicity, aromaticity, and molecular weight of the U. pertusa-DOM increase during the 27-day incubation period. Fluorescence excitation-emission matrix spectroscopy combined with parallel factor analysis suggests that the relative abundance of the protein-like component (C1) (96.10-84.96%) sequentially decreases, whereas the humic-like components (C2) (2.16-9.73%) and (C3) (1.75-5.31%) in the U. pertusa-DOM increase with the U. pertusa decomposition. The Cu(II) binding properties of the U. pertusa-DOM are dependent on the decomposition time. The order of the conditional stability constant (logKM) is C2 > C1 > C3. The complexation capacity (f) of C1 is higher than those of C2 and C3 at a specific time. Synchronous fluorescence spectroscopy coupled with two-dimensional correlation spectroscopy reveals that the microbial degradation could accelerate the Cu(II) binding to humic-like fractions in the U. pertusa-DOM. These findings will help us better understand the biogeochemical behaviors of macroalgal DOM and heavy metal in coastal ecosystems.

Optimizing biomethane production of mesophilic chicken manure and sheep manure digestion: Mono-digestion and co-digestion kinetic investigation, autofluorescence analysis and microbial community assessment.

Optimization of mesophilic methane production from Chicken manure (CM) and Sheep manure (SM) at total solid (TS) of 8% and 1.6% were obtained by sequence tests in mono-digestion. However, the positive synergy of co-digestion with an optimum CM/SM of 2.5 (310 mLCH4/gVSadded) resulted in a high hydrolytic capacity and methane production. The modified Gompertz model (R2 > 0.98) and modified Aiba model (R2 > 0.88) illustrated co-digestion significantly improved the methane generation rate with strong ammonia tolerance. Dissolved Organic Matter (DOM) variation in response to the metabolic rate of microbial community illustrated that the SMP-like and protein-like components half-split by EEM-PARAFAC were significantly negative corresponded to bio-methane production. Moreover, the canonical correlation analysis (CCA) resulted a significant difference between the substrate and DOM composition. Potential functional metabolic illustrated statistically significance difference between mono and co-digestion, however, Methanosaeta and Syntrophobacter predominated the syntrophic methanogenesis. The constructed complex metabolic cooperation caused the co-digestion stable and high efficiency.

Effects of intercropping mulch on the content and composition of soil dissolved organic matter in apple orchard on the loess plateau.

Dissolved organic matter (DOM) is an important parameter that reflects soil fertility and quality. In this study, the effects of intercropping perennial ryegrass and straw mulch on the content, composition and spectral characteristics of soil DOM in orchards in arid and semi-arid areas were investigated by three-dimensional fluorescence excitation-emission matrix (EEM) combined with parallel factor analysis (PARAFAC). Three treatments were applied in a 6-year-old apple orchard on the Loess Plateau: (1) clean tillage (CT); (2) intercropping perennial ryegrass mulch (RE); (3) intercropping straw mulch (CS). Soil samples (0-10, 10-20, 20-40, 40-60, 60-80, 80-100 cm) were collected from different treatments. The total soil organic carbon (SOC) and dissolved organic carbon (DOC) content were ranked as CS> RE> CT, and decreased with soil depth. In addition, the vertical distribution of DOC with different soil depth was caused by organic matter input but not leaching. Three humic-like components and two protein-like components were identified by EEM-PARAFAC. Fluorescence spectra showed that humic-like compounds were the dominant fractions in soil DOM in the CS treatment. Fluorescence Index (FI) indicated that the proportion of plant residues and soil organic matter derived DOM ranked as CT> RE> CS and gradually decreased with soil depth. Our results highlight the key role of orchard intercropping mulch in improving the content and compositions of soil DOM through different forms of organic inputs and provide new theoretical support for the evaluation of soil fertility in orchards.

Organic carbon source-dependent properties of soluble microbial products in sequencing batch reactors and its effects on membrane fouling.

This study investigated the influence of three different organic carbon sources including sodium acetate (SOD), glucose (GLU), and starch (STAR), on soluble microbial products (SMP), which presumably have dissimilar uptake rates and metabolic pathways, in sequencing batch reactors (SBR) and their subsequent effects on membrane fouling of ultrafiltration (UF). SMP were mainly characterized by fluorescence excitation emission matrix coupled with parallel factor analysis (EEM-PARAFAC) and size exclusion chromatography (SEC). SMP produced in SOD-fed SBR showed higher abundances of protein-like fluorescent component and large sized aliphatic biopolymer (BP) than GLU- or STAR-fed counterpart did, while the STAR-based operation resulted in more SMP enriched with humic-like fluorescence. The differences in SMP exerted marked effects on UF membrane fouling as indicated by the highest fouling potential with reversibility shown for the SMP from the SOD-fed reactor. Regardless of the carbon source, BP fraction and protein-like component exhibited the greatest extent of reversible fouling, suggesting that size exclusion plays a critical role. However, notable differences in the reversible fouling propensity of relatively smaller size fractions among the three SBRs signified the possible involvement of chemical interactions as a secondary fouling mechanism and its dependency on different carbon sources. Our results provide a new insight into the roles of carbon sources in the characteristics of SMP in biological treatment systems and their effects on the post-treatment using membrane filtration, which is ultimately beneficial to the optimization of biological treatment design and membrane filtration operation.

Using fluorescence surrogates to track algogenic dissolved organic matter (AOM) during growth and coagulation/flocculation processes of green algae.

Tracking the variation of the algogenic organic matter (AOM) released during the proliferation of green algae and subsequent treatment processes is crucial for constructing and optimizing control strategies. In this study, the potential of the spectroscopic tool was fully explored as a surrogate of AOM upon the cultivation of green algae and subsequent coagulation/flocculation (C/F) treatment processes using ZrCl4 and Al2(SO4)3. Fluorescence excitation emission matrix coupled with parallel factor analysis (EEM-PARAFAC) identified the presence of three independent fluorescent components in AOM, including protein-like (C1), fulvic-like (C2) and humic-like components (C3). Size exclusion chromatography (SEC) revealed that C1 in AOM was composed of large-sized proteins and aromatic amino acids. The individual components exhibited their unique characteristics with respect to the dynamic changes. C1 showed the highest correlation with AOM concentrations (R2 = 0.843) upon the C/F processes. C1 could also be suggested as an optical predictor for the formation of trihalomethanes upon the C/F processes. This study sheds a light for the potential application of the protein-like component (C1) as a practical surrogate to track the evolution of AOM in water treatment or wastewater reclamation systems involving Chlorella vulgaris green algae.

Importance of nutrient availability for soluble microbial products formation during a famine period of activated sludge: Evidence from multiple analyses.

Much remains unknown about compositional variations in soluble microbial products (SMP) with the shift of the substrate condition from a feast to a famine phase in biological treatment systems. This study demonstrated that the formation of SMP could be suppressed by up to 75% during the famine phase with the addition of essential nutrients. In contrast, presence of electron acceptor did not play any significant role during the stress condition, showing the similar amounts of SMP (r = 0.98, p < 0.05) formation between the bioreactors supplied with air and N2. The SMP formed in the famine phase was more bio-refractory in the famine versus the feast phase with a linear correlation shown between the production and their aromatic structures in the composition (R2 > 0.95). The fluorescence excitation-emission matrix coupled with parallel factor analysis (EEM-PARAFAC) revealed the presence of four different fluorescent components, including two protein-like (C1 and C4), fulvic-like (C2), and humic-like (C3) components, in the SMP and bEPS formed at different conditions. Both C1 and C4 showed increasing trends (R2 > 0.95) with the length of starvation in the bioreactors without essential nutrients. Nutrient availability was found to be a key factor to quench the production of large-sized biopolymers. This study provides a wealth of information on operation conditions of activated sludge treatment systems to minimize large sized SMP molecules (particularly proteins), which typically exert many environmental concerns to effluent organic matter quality.

Effect of photo-biodegradation and biodegradation on the biogeochemical cycling of dissolved organic matter across diverse surface water bodies.

The objective of this research was to quantify the temporal variation of dissolved organic matter (DOM) in five distinct waterbodies in watersheds with diverse types of land use and land cover in the presence and absence of sunlight. The water bodies were an agricultural pond, a lake in a forested watershed, a man-made reservoir, an estuary, and a bay. Two sets of samples were prepared by dispensing unfiltered samples into filtered samples in 1:10 ratio (V/V). The first set was exposed to sunlight (10 hr per day for 30 days) for examining the combined effect of photo-biodegradation, while the second set was stored in dark for examining biodegradation alone. Spectroscopic measurements in tandem with multivariate statistics were used to interpret DOM lability and composition. The results suggest that the agricultural pond behaved differently compared to other study locations during degradation experiments due to the presence of higher amount of microbial humic-like and protein-like components derived from microbial/anthropogenic sources. For all samples, a larger decrease in dissolved organic carbon (DOC) concentration (10.12% ±â€¯9.81% for photo-biodegradation and 6.65% ±â€¯2.83% for biodegradation) and rapid transformation of DOM components (i.e., terrestrial humic-like components into microbial humic and protein-like components) were observed during photo-biodegradation experiments. Results suggest that sunlight facilitated DOM biodegradation, resulting in simpler recalcitrant molecules regardless of original composition. Overall, it was found that combined effects of light and bacteria are more efficient than bacterial effects alone in remineralizing and altering DOM, which highlights the crucial importance of sunlight in transforming aquatic DOM.

Insight into the heterogeneous adsorption of humic acid fluorescent components on multi-walled carbon nanotubes by excitation-emission matrix and parallel factor analysis.

The heterogeneous adsorption behavior of commercial humic acid (HA) on pristine and functionalized multi-walled carbon nanotubes (MWCNTs) was investigated by fluorescence excitation-emission matrix and parallel factor (EEM- PARAFAC) analysis. The kinetics, isotherms, thermodynamics and mechanisms of adsorption of HA fluorescent components onto MWCNTs were the focus of the present study. Three humic-like fluorescent components were distinguished, including one carboxylic-like fluorophore C1 (λex/λem= (250, 310) nm/428nm), and two phenolic-like fluorophores, C2 (λex/λem= (300, 460) nm/552nm) and C3 (λex/λem= (270, 375) nm/520nm). The Lagergren pseudo-second-order model can be used to describe the adsorption kinetics of the HA fluorescent components. In addition, both the Freundlich and Langmuir models can be suitably employed to describe the adsorption of the HA fluorescent components onto MWCNTs with significantly high correlation coefficients (R2> 0.94, P< 0.05). The dissimilarity in the adsorption affinity (Kd) and nonlinear adsorption degree from the HA fluorescent components to MWCNTs was clearly observed. The adsorption mechanism suggested that the π-π electron donor-acceptor (EDA) interaction played an important role in the interaction between HA fluorescent components and the three MWCNTs. Furthermore, the values of the thermodynamic parameters, including the Gibbs free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°), showed that the adsorption of the HA fluorescent components on MWCNTs was spontaneous and exothermic.

Assessing the environmental impact of phenanthrene in different types of land use based on the binding characteristics with dissolved organic matter.

The binding characteristics of phenanthrene with dissolved organic matter (DOM) were studied by the excitation emission matrix fluorescence spectroscopy with parallel factor analysis in four types of land use which derived from forest (F), meadow (M), cropland (C), and greenhouse (G). The results showed that the humification degree and binding characteristics of phenanthrene with DOM were distinct differences in the four soils. The binding capacities of humic-like components with phenanthrene were stronger than those of protein-like components. The log K derived from the Stern-Volmer equation significantly correlated with the humification degree of DOM (p < 0.05) in different types of land use. Besides, correlation analysis demonstrated that the potential binding index (Fk) obtained from the modified Stern-Volmer model was a more accurate parameter to describe the combination degree of DOM with phenanthrene than log K, which presented a decrease order of C > F > M > G. Therefore, the environmental impact of phenanthrene in different types of land use could be assessed deeply based on the Fk and DOM concentration.

Characterization of atrazine binding to dissolved organic matter of soil under different types of land use.

Atrazine is widely used in agriculture. In this study, dissolved organic matter (DOM) from soils under four types of land use (forest (F), meadow (M), cropland (C) and wetland (W)) was used to investigate the binding characteristics of atrazine. Fluorescence excitation-emission matrix-parallel factor (EEM-PARAFAC) analysis, two-dimensional correlation spectroscopy (2D-COS) and Stern-Volmer model were combined to explore the complexation between DOM and atrazine. The EEM-PARAFAC indicated that DOM from different sources had different structures, and humic-like components had more obvious quenching effects than protein-like components. The Stern-Volmer model combined with correlation analysis showed that log K values of PARAFAC components had a significant correlation with the humification of DOM, especially for C3 component, and they were all in the same order as follows: meadow soil (5.68)>wetland soil (5.44)>cropland soil (5.35)>forest soil (5.04). The 2D-COS further confirmed that humic-like components firstly combined with atrazine followed by protein-like components. These findings suggest that DOM components can significantly influence the bioavailability, mobility and migration of atrazine in different land uses.