Reduction of organic contaminants from industrial effluent using the advanced oxidation process, chemical coagulation, and green nanotechnology.

Municipal wastewater treatment systems use the chemical oxygen demand test (COD) to identify organic contaminants in industrial effluents that impede treatment due to their high concentration. This study reduced the COD levels in tannery wastewater using a multistage treatment process that included Fenton oxidation, chemical coagulation, and nanotechnology based on a synthetic soluble COD standard solution. At an acidic pH of 5, Fenton oxidation reduces the COD concentration by approximately 79%. It achieves this by combining 10 mL/L of H2O2 and 0.1 g/L of FeCl2. Furthermore, the author selected the FeCl3 coagulant for the coagulation process based on the best results of comparisons between different coagulants. At pH 8.5, the coagulation dose of 0.15 g/L achieved the maximum COD removal efficiency of approximately 56.7%. Finally, nano bimetallic Fe/Cu was used to complete the degradation and adsorption of the remaining organic pollutants. The XRD, SEM, and EDX analyses proved the formation of Fe/Cu nanoparticles. A dose of 0.09 g/L Fe/Cu NPs, 30 min of contact time, and a stirring rate of 200 rpm achieve a maximum removal efficiency of about 93% of COD at pH 7.5. The kinetics studies were analyzed using pseudo-first-order P.F.O., pseudo-second-order P.S.O., and intraparticle diffusion models. The P.S.O. showed the best fit among the kinetic models, with an R2 of 0.998. Finally, the authors recommended that technique for highly contaminated industrial effluents treatment for agriculture or industrial purposes.

Machine learning for high-precision simulation of dissolved organic matter in sewer: Overcoming data restrictions with generative adversarial networks.

Understanding the transformation process of dissolved organic matter (DOM) in the sewer is imperative for comprehending material circulation and energy flow within the sewer. The machine learning (ML) model provides a feasible way to comprehend and simulate the DOM transformation process in the sewer. In contrast, the model accuracy is limited by data restriction. In this study, a novel framework by integrating generative adversarial network algorithm-machine learning models (GAN-ML) was established to overcome the drawbacks caused by the data restriction in the simulation of the DOM transformation process, and humification index (HIX) was selected as the output variable to evaluate the model performance. Results indicate that the GAN algorithm's virtual dataset could generally enhance the simulation performance of regression models, deep learning models, and ensemble models for the DOM transformation process. The highest prediction accuracy on HIX (R2 of 0.5389 and RMSE of 0.0273) was achieved by the adaptive boosting model which belongs to ensemble models trained by the virtual dataset of 1000 samples. Interpretability analysis revealed that dissolved oxygen (DO) and pH emerge as critical factors warranting attention for the future development of management strategies to regulate the DOM transformation process in sewers. The integrated framework proposed a potential approach for the comprehensive understanding and high-precision simulation of the DOM transformation process, paving the way for advancing sewer management strategy under data restriction.

The molecular binding sequence transformation of soil organic matter and biochar dissolved black carbon antagonizes the transport of 2,4,6-trichlorophenol.

Dissolved organic matter (DOM) and dissolved black carbon (DBC) are significant environmental factors that influence the transport of organic pollutants. However, the mechanisms by which their molecular diversity affects pollutant transport remain unclear. This study elucidates the molecular binding sequence and adsorption sites through which DOM/DBC compounds antagonize the transport of 2,4,6-trichlorophenol (TCP) using column experiments and modelling. DBC exhibits a high TCP adsorption rate (kn = 5.32 × 10-22 mol1-n∙Ln-1∙min-1) and conditional stability constant (logK = 5.19-5.74), indicating a strong binding affinity and antagonistic effect on TCP. This is attributed to the high relative content of lipid/protein compounds in DBC (25.65 % and 30.28 %, respectively). Moreover, the small molecule lipid compounds showed stronger TCP adsorption energy (Ead = -0.0071 eV/-0.0093 eV) in DOM/DBC, combined with two-dimensional correlation spectroscopy model found that DOM/DBC antagonized TCP transport in the environment through binding sequences that transformed from lipid/protein small molecule compounds to lignin/tannin compounds. This study used a multifaceted approach to comprehensively assess the impact of DOM/DBC on TCP transport. It reveals that the molecular diversity of DOM/DBC is a critical factor affecting pollutant transport, providing important insights into the environmental trend and ecological effects of pollutants.

Effects of dissolved organic matter on distribution characteristics of heavy metals and their interactions with microorganisms in soil under long-term exogenous effects.

Long-term waste accumulation (LTWA) in soil not only alters its physical and chemical properties but also affects heavy metals and microorganisms in polluted soil through the dissolved organic matter (DOM) it produces. However, research on the impact of DOM from LTWA on heavy metals and microorganisms in polluted soil is limited, which has resulted in an incomplete understanding of the mechanisms involved in LTWA soils remediation. This study focuses on the DOM generated by waste accumulation and analyses the physicochemical properties, microbial community structure, and vertical distribution of heavy metals in four types of LTWA soils at different depths (0-100 cm). A causal analysis is conducted using structural equation modelling. The results indicate that due to the retention effect of the soil and microorganisms, heavy metal pollution is concentrated on the soil surface layer (>30 cm). With increasing depth, there is a decrease in heavy metal concentration and an increase in microbial diversity and abundance. DOM plays a significant role in regulating the concentration of soil heavy metals and the diversity and abundance of microorganisms. The DOM from different soils gradually transforms into substances dominated by tyrosine, tryptophan, and fulvic acid, which sustain the normal life activities and gene expression of microorganisms. Bacteria such as Pseudarthrobacter, Desulfurivibrio, Thiobacillus, and Sulfurimonas, which are involved in energy transformation, along with genes such as water channel protein and YDIF, which enhance heavy metal metabolism, ensure that microbial communities can maintain basic life processes in polluted environments and gradually select for dominant species that are adapted to heavy metal pollution. These novel discoveries illuminate the potential for modulating the composition of DOM to amplify microbial activity, while concurrently offering insights into the migration patterns of various long-term exogenous pollutants. This foundational knowledge provides a foundation for the development of efficacious remediation strategies.

Identifying the fate of dissolved organic matter in wastewater treatment plant effluent-dominated urban river based on fluorescence fingerprinting and flux budget approach.

Effluent organic matter from wastewater treatment plants (WWTPs) is an important source of dissolved organic matter (DOM) in urban rivers worldwide and is an important water quality factor. Identifying the fate of DOM in urban river is crucial for water quality management. To address this concern, a fluorescent flux budget approach was conducted to probe the fate of DOM in WWTP effluent-dominated urban river, in combination with field measurement and fluorescence fingerprinting. An urban river receiving two WWTP effluents in Hefei City, China was chosen as the study site, where longitudinal measurements of river hydrology and water quality were performed. The fluorescence fingerprinting revealed the presence of two humic-like components (C1, C4), one fulvic-like component (C2) and one protein-like component (C3) in this investigated river, among which C2 and C4 were indicative of anthropogenic influences, closely associated with treated effluents. For each fluorescent component, the WWTP effluent contributed over 80 % of the total fluorescent dissolved organic matter (FDOM) input in this river. Using the developed FDOM flux budget model, it was found that the C1 and C3 were almost conserved within the waterbody, while the C2 and C4 experienced losses due to biogeochemical reactions. The decay rates of C2 and C4 were estimated to be 0.109-0.174 d-1 and 0.096-0.320 d-1, respectively. Spatial heterogeneity of decay rates for C2 and C4 were associated with the varied chemistries of the lateral input sources including two treated effluents and one tributary flow. Our study highlights that after treated effluent is released into the receiving waterbody, the FDOM would undergo loss from the waters particularly for anthropogenic fulvic-like substance C2 and humic-like substance C4. Additionally, the quantified FDOM decay rate in actual urban water environment provides insights for river water quality management, especially when using DOM as the surrogate indicator of organic pollutants.

Comparative investigation of known and unknown disinfection by-product precursor removal and microbial community from biological biochar and activated carbon filters.

Biological activated carbon filter (BAC) is one of the most effective technologies for removing disinfection by-product (DBP) precursors from water. Biochar is a lower-cost medium that has the potential to replace granular activated carbon in BAC applications, thus leading to the development of biological biochar filter (BCF). This study compared BCF with BAC for the removal of DBP precursors using column experiments. Both BCF and BAC achieved the removal of DBP precursors, resulting in concentrations of all DBP formation potential below the World Health Organization guideline values for drinking water. Bromodichloromethane and unknown DBP precursor removal by BCF was comparable to that by BAC. However, BAC removed more chloroform and dichloroacetontrile precursors than BCF. For microbial community analysis, cell numbers in a bottom layer (inlet) of BCF and BAC columns were higher than those in the top layer. The abundances of Nordella and a microbial genus from Burkholderiaceae at the bottom layer showed a strong correlation to the number of DBP precursors removed and were comparable in BCF and BAC. This finding likely contributes to the similarities between DBPs species removed and the removal performances of some known and unknown DBP precursors by BCF and BAC. Overall results from this study revealed that biochar can be served as a low-cost and sustainable replacement of activated carbon in water filter for DBP precursor removal.

Arsenic distribution characteristics and release mechanisms in aquaculture lake sediments.

It is well known that aquaculture can alter the microenvironments of lakes at sediment-water interface (SWI). However, the main mechanisms underlying the effects of aquaculture activities on arsenic (As) transformations are still unclear. In this context, the present study aims to investigate the variations in the sediment As contents in Yangcheng Lake, as well as to assess its chemical transformations, release fluxes, and release mechanisms. The results showed substantial spatial differences in the dissolved As concentrations in the sediment pore water. The As release fluxes at the SWI ranged from 1.32 to 112.09 µg/L, with an average value of 33.68 µg/L. In addition, the highest As fluxes were observed in the aquaculture areas. The transformation of crystalline hydrous Fe oxide-bound As to adsorbed-As in the aquaculture lake sediments increased the ability of As release. The Partial least squares path modeling results demonstrated the great contributions of organic matter (OM) to the As transformations by influencing the sediment microbial communities and Fe/Mn minerals. The changes in the As fractionation and competing adsorption increased the dissolved As concentrations in the 0-10 mm surface sediment. Non-specifically and specifically adsorbed As were the major sources of dissolved As in the sediments. Specifically, microbial reduction of As[V] and dissolution of Fe oxides increased the dissolved As concentrations at the SWI (20 to -20 mm). The results of the current study highlight the positive enhancement effects of aquaculture on As release from sediments.

Natural Attenuation of Groundwater Uranium in Post-Neutral-Mining Sites Evidenced from Multiple Isotopes and Dissolved Organic Matter.

Although natural attenuation is an economic remediation strategy for uranium (U) contamination, the role of organic molecules in driving U natural attenuation in postmining aquifers is not well-understood. Groundwaters were sampled to investigate the chemical, isotopic, and dissolved organic matter (DOM) compositions and their relationships to U natural attenuation from production wells and postmining wells in a typical U deposit (the Qianjiadian U deposit) mined by neutral in situ leaching. Results showed that Fe(II) concentrations and δ34SSO4 and δ18OSO4 values increased, but U concentrations decreased significantly from production wells to postmining wells, indicating that Fe(III) reduction and sulfate reduction were the predominant processes contributing to U natural attenuation. Microbial humic-like and protein-like components mediated the reduction of Fe(III) and sulfate, respectively. Organic molecules with H/C > 1.5 were conducive to microbe-mediated reduction of Fe(III) and sulfate and facilitated the natural attenuation of dissolved U. The average U attenuation rate was -1.07 mg/L/yr, with which the U-contaminated groundwater would be naturally attenuated in approximately 11.2 years. The study highlights the specific organic molecules regulating the natural attenuation of groundwater U via the reduction of Fe(III) and sulfate.

Intraspecific variation in crayfish behavioral traits affects leaf litter breakdown in streams.

Although intraspecific trait variation is increasingly recognized as affecting ecosystem processes, few studies have examined the ecological significance of among-population variation in behavioral traits in natural ecosystems. In freshwater habitats, crayfish are consumers that can influence ecosystem structure (e.g., macroinvertebrate communities) and function (e.g., leaf litter breakdown). To test whether crayfish behavioral traits (activity, boldness, and foraging voracity) are major contributors of leaf litter breakdown rates in the field, we collected rusty crayfish (Faxonius rusticus) from eight streams across the midwestern USA and measured behaviors using laboratory assays. At the same streams, we measured breakdown rates of leaf packs that were accessible or inaccessible to crayfish. Our results provide evidence that among-population variation in crayfish boldness and foraging voracity was a strong predictor of leaf litter breakdown rates, even after accounting for commonly appreciated environmental drivers (water temperature and human land use). Our results suggest that less bold rusty populations (i.e., emerged from shelter more slowly) had greater direct impacts on leaf litter breakdown than bold populations (P = 0.001, r2 = 0.85), potentially because leaf packs can be both a shelter and food resource to crayfish. Additionally, we found that foraging voracity was negatively related to breakdown rates in leaf packs that were inaccessible to crayfish (P = 0.025, r2 = 0.60), potentially due to a trophic cascade from crayfish preying on other invertebrates that consume leaf litter. Overall, our results add to the growing evidence that trait variation in animals may be important for understanding freshwater ecosystem functioning.

Unexpected contributions by carbonates and organic matter in a silicate-dominated tropical catchment: An isotope approach.

The understanding of global carbon has rarely extended to small-scale tropical river basins. To address these uncertainties, this study aims to investigate the importance of rock weathering and organic matter turnover in the carbon cycle in a terrain dominated by crystalline silicate rocks. The geochemical composition of the dissolved and particulate carbon phases (DIC, DOC and POC) and their stable carbon isotopes were studied in the Deduru Oya River in Sri Lanka. Dissolved inorganic carbon (DIC) was the most dominant carbon phase and its contribution to the total carbon pool varied between 67 and 89 %. Furthermore, the δ13CDIC values in the river varied between -1.1 and -16.5 ‰. The lithological characteristics and molar ratios between Ca2+, Mg2+ and HCO3- indicated rock weathering mainly by CO2 and carbonic acid. The δ13CDIC values for groundwater input were -15.9 ‰, while for carbonate weathering, mainly due to fertiliser input, they reached a value of -12.7 ‰. This input was fed into an isotope mass balance to determine the relative contributions. However, the isotope mass balance was only plausible after correcting for the effects on the δ13CDIC caused by degassing and photosynthesis. Our study demonstrated that carbonate weathering and organic matter turnover are essential components of the river carbon cycle even in a silicate dominated catchment. They can represent up to 60 % of the DIC pool. Combined with the higher organic matter turnover and high pCO2 in the river water, it can be suggested that the Deduru Oya River acts as a net source of CO2 in the atmosphere. Our study shows that CO2 degassing and in-stream photosynthesis in tropical river systems need to be considered along with chemical weathering to account for carbon transport and turnover in tropical rivers.

Nanoscale Sequential Reactor Design Achieves Effective Removal of Disinfection Byproduct Precursors in Catalytic Ozonation.

Transforming dissolved organic matter (DOM) is a crucial approach to alleviating the formation of disinfection byproducts (DBPs) in water treatment. Although catalytic ozonation effectively transforms DOM, increases in DBP formation potential are often observed due to the accumulation of aldehydes, ketones, and nitro compound intermediates during DOM transformation. In this study, we propose a novel strategy for the sequential oxidation of DOM, effectively reducing the levels of accumulation of these intermediates. This is achieved through the development of a catalyst with a tailored surface and nanoconfined active sites for catalytic ozonation. The catalyst features a unique confinement structure, wherein Mn-N4 moieties are uniformly anchored on the catalyst surface and within nanopores (5-20 Å). This design enables the degradation of the large molecular weight fraction of DOM on the catalyst surface, while the transformed smaller molecular weight fraction enters the nanopores and undergoes rapid degradation due to the confinement effect. The generation of *Oad as the dominant reactive species is essential for effectively reducing these ozone refractory intermediates. This resulted in over 70% removal of carbonaceous and nitrogenous DBP precursors as well as brominated DBP precursors. This study highlights the importance of the nanoscale sequential reactor design and provides new insights into eliminating DBP precursors by the catalytic ozonation process.

Microbially Driven Iron Cycling Facilitates Organic Carbon Accrual in Decadal Biochar-Amended Soil.

Soil organic carbon (SOC) is pivotal for both agricultural activities and climate change mitigation, and biochar stands as a promising tool for bolstering SOC and curtailing soil carbon dioxide (CO2) emissions. However, the involvement of biochar in SOC dynamics and the underlying interactions among biochar, soil microbes, iron minerals, and fresh organic matter (FOM, such as plant debris) remain largely unknown, especially in agricultural soils after long-term biochar amendment. We therefore introduced FOM to soils with and without a decade-long history of biochar amendment, performed soil microcosm incubations, and evaluated carbon and iron dynamics as well as microbial properties. Biochar amendment resulted in 2-fold SOC accrual over a decade and attenuated FOM-induced CO2 emissions by approximately 11% during a 56-day incubation through diverse pathways. Notably, biochar facilitated microbially driven iron reduction and subsequent Fenton-like reactions, potentially having enhanced microbial extracellular electron transfer and the carbon use efficiency in the long run. Throughout iron cycling processes, physical protection by minerals could contribute to both microbial carbon accumulation and plant debris preservation, alongside direct adsorption and occlusion of SOC by biochar particles. Furthermore, soil slurry experiments, with sterilization and ferrous iron stimulation controls, confirmed the role of microbes in hydroxyl radical generation and biotic carbon sequestration in biochar-amended soils. Overall, our study sheds light on the intricate biotic and abiotic mechanisms governing carbon dynamics in long-term biochar-amended upland soils.

Reduction of the exchangeable cadmium content in soil by appropriately increasing the maturity degree of organic fertilizers.

To enhance the remediation effect of heavy metal pollution, organic fertilizers with different maturity levels were added to cadmium-contaminated soil. The remediation effect was determined by evaluating the form transformation and bioavailability of cadmium in heavy metal-contaminated soil. -Results showed that when the maturity was 50%, although the soil humus (HS) content increased, it didn't contribute to reducing the bioavailability of soil Cd. Appropriately increasing the maturity (GI ≥ 80%), the HS increased by 113.95%∼157.96%, and reduced significantly the bioavailability of soil Cd, among the exchangeable Cd decreased by 16.04%∼33.51% (P < 0.01). The structural equation modeling (SEM) revealed that HS content is a critical factor influencing the transformation of Cd forms and the reduction of exchangeable Cd accumulation; the HS and residual Cd content were positively correlated with the maturity (P < 0.01), while exchangeable Cd content was negatively correlated with maturity (P < 0.01), and the correlation increased with increasing maturity. In summary, appropriately increasing the maturity (GI ≥ 80%) can increase significantly HS, promote the transformation of exchangeable Cd into residual Cd, and ultimately enhance the effectiveness of organic fertilizers in the remediation of soil Cd pollution. These results provide a new insight into the remediation of Cd-contaminated soil through organic fertilizer as soil amendment in Cd-contaminated soil.

Enhancing Molecular Characterization of Dissolved Organic Matter by Integrative Direct Infusion and Liquid Chromatography Nontargeted Workflows.

Dissolved organic matter (DOM) in aquatic systems is a highly heterogeneous mixture of water-soluble organic compounds, acting as a major carbon reservoir driving biogeochemical cycles. Understanding DOM molecular composition is thus of vital interest for the health assessment of aquatic ecosystems, yet its characterization poses challenges due to its complex and dynamic chemical profile. Here, we performed a comprehensive chemical analysis of DOM from highly urbanized river and seawater sources and compared it to drinking water. Extensive analyses by nontargeted direct infusion (DI) and liquid chromatography (LC) high-resolution mass spectrometry (HRMS) through Orbitrap were integrated with novel computational workflows to allow molecular- and structural-level characterization of DOM. Across all water samples, over 7000 molecular formulas were calculated using both methods (∼4200 in DI and ∼3600 in LC). While the DI approach was limited to molecular formula calculation, the downstream data processing of MS2 spectral information combining library matching and in silico predictions enabled a comprehensive structural-level characterization of 16% of the molecular space detected by LC-HRMS across all water samples. Both analytical methods proved complementary, covering a broad chemical space that includes more highly polar compounds with DI and more less polar ones with LC. The innovative integration of diverse analytical techniques and computational workflow introduces a robust and largely available framework in the field, providing a widely applicable approach that significantly contributes to understanding the complex molecular composition of DOM.

Metagenomic and FT-ICR MS insights into the mechanism for the arsenic biogeochemical cycling in groundwater.

Arsenic (As) is a groundwater contaminant of global concern. The degradation of dissolved organic matter (DOM) can provide a reducing environment for As release. However, the interaction of DOM with local microbial communities and how different sources and types of DOM influence the biotransformation of As in aquifers is uncertain. This study used optical spectroscopy, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), metagenomics, and structural equation modeling (SEM) to demonstrate the how the biotransformation of As in aquifers is promoted. The results indicated that the DOM in high-As groundwater is dominated by highly unsaturated low-oxygen(O) compounds that are quite humic and stable. Metagenomics analysis indicated Acinetobacter, Pseudoxanthomonas, and Pseudomonas predominate in high-As environments; these genera all contain As detoxification genes and are members of the same phylum (Proteobacteria). SEM analyses indicated the presence of Proteobacteria is positively related to highly unsaturated low-O compounds in the groundwater and conditions that promote arsenite release. The results illustrate how the biogeochemical transformation of As in groundwater systems is affected by DOM from different sources and with different characteristics.

Silver sulfide nanoparticles eliminate the stimulative effects of earthworms on nutrient uptake by soybeans in high organic matter soils.

A significant knowledge gap exists regarding the impact of soil organic matter on the bioavailability of Ag2S-NPs (environmentally relevant forms of Ag-NPs) in soil-earthworm-plant systems. This study used two soils with varying organic matter content, both with and without earthworms, to investigate the bioavailability of Ag2S-NPs. The findings revealed an 80 % increase in Ag bioaccessibility to soybeans in soils with high organic matter content compared to soils with low organic matter. Additionally, the presence of earthworms significantly increased Cl concentrations from 24.3-62.2 mg L-1 to 80.1-147.2 mg L-1, triggering the elevated bioavailability of Ag. Interestingly, Ag2S-NPs eliminated the stimulative effects of earthworms on plant nutrient uptake. In the presence of earthworms, the high organic matter soil amended with Ag2S-NPs exhibited lower concentrations of essential elements (Ca, Cu, Fe, K, and P) in plant tissues compared to soils without earthworms. Our study presents evidence of the transformation of Ag2S-NPs into Ag-NPs across various soil solutions, resulting in the formation of Ag nanoparticle complexes. Particularly noteworthy is the significant reduction in particle sizes in soils incubated with earthworms and high organic matter content, from 85.0 nm to 40.2 nm. Notably, in the rhizosphere soil, a decrease in the relative abundance of nutrient cycling-related phyla was observed, with reductions of 18.5 % for Proteobacteria and 30.0 % for Actinobacteriota. These findings offer valuable insights into the biological and biochemical consequences of Ag2S-NP exposure on earthworm-mediated plant nutrient acquisition.

Comparison of UV/PS and VUV/PS as ultrafiltration pretreatment: Performance, mechanisms, DBPs formation and toxicity assessment.

Ultrafiltration (UF) is widely used in drinking water plants, nevertheless, it still encounters challenges stemming from inevitable membrane fouling caused by natural organic matter (NOM). Herein, this work applied VUV/PS as UF membrane pretreatment and used UV/PS for comparison. VUV/PS system exhibited superior ability in removing NOM compared to UV/PS system. HO and SO4- played crucial roles in the degradation. [SO4-]ss was notably higher than [HO]ss in the systems, yet HO was of greater significance. [HO]ss and [SO4-]ss in the VUV/PS process were remarkably higher than those in the UV/PS process, due to the function of 185 nm photons. VUV/PS pretreatment basically recovered flux and effectively reduced fouling resistance, with better performance than UV/PS. Fouling mechanism was dominated by multiple mechanisms after UV/PS pretreatment, whereas it was transformed into pore blockage after VUV/PS pretreatment. Moreover, the UF effluent quality after VUV/PS pretreatment outperformed that of UV/PS but fell short of that without pretreatment, possibly due to the generation of abundant low MW substances under the action of HO and SO4-. After chlorine disinfection, UV/PS and VUV/PS pretreatments increased the DBPs production and cytotoxicity. Specifically, oxidant PS affected the membrane surface morphology and fouling behaviors, and had no obvious effect on interception performance and mechanical properties. In actual water treatment, VUV/PS and UV/PS pretreatments exhibited excellent performance in alleviating membrane fouling, improving water quality, and reducing DBPs formation and acute toxicity.

Adsorption behaviors of perfluorooctanoic acid on aged microplastics.

The presence of perfluoroalkyl substances (PFAS) in the environment poses a significant threat to ecological safety and environmental health. Widespread microplastics (MPs) have been recognized as vectors for emerging contaminants due to human activities. However, the adsorption behaviors of PFAS on MPs, especially on aged MPs, have not been extensively investigated. This study aimed to investigate the adsorption behaviors of perfluorooctanoic acid (PFOA) on aged MPs (polystyrene, polyethylene, and polyethylene terephthalate) treated with UV irradiation and persulfate oxidation under salinity and dissolve organic matter (DOM) condition. Carbonyl index values of MPs increased after the aged treatment, indicating the production of oxygen-containing groups. The PFOA adsorption on aged MPs was impacted by the co-existence of Na+ ions and DOM. As PFOA adsorption onto aged MPs was mainly controlled by hydrophobic interaction, the electrostatic interaction also made a contribution, but there was no significant change in PFOA adsorption behavior between the pristine and aged MPs. While these findings provide insight into PFAS adsorption on aged MPs, further research is necessary to account for the complexity of the real environment. PRACTITIONER POINTS: Adsorption behaviors of perfluorooctanoic acid (PFOA) on aged microplastics were investigated. Hydrophobic interaction mainly controlled PFOA adsorption on aged microplastics (MPs). Co-existence dissolve organic matter and salinity influenced PFOA adsorption behaviors on aged MPs.

Biodegradation of mixed litter-derived dissolved organic matter with varying evenness in a temperate freshwater wetland.

Litter-derived dissolved organic matter (DOM) plays an essential role in biogeochemical cycles. In wetlands, species relative abundance and its change have great influences on input features of litter-derived DOM, including chemical characteristics per se and functional diversity of chemical characteristics. Functional diversity is an important factor controlling organic matter biodegradation, but little is known in terms of the DOM. We mixed litter leachates of four macrophytes with a constant concentration (20 mg DOC L-1) but varying dominant species and volume ratios, i.e. 15:1:1:1 (low-evenness), 5:1:1:1 (mid-evenness), and 2:1:1:1 (high-evenness), generating a gradient of chemical characteristics and functional diversity (represented by functional dispersion index FDis). Based on a 42-d incubation, we measured degradation dynamics of these DOM mixtures, and analyzed potential determinants. After 42 days of incubation, the high-evenness treatments, along with mid-evenness treatments sometimes, had most degradation, while the low-evenness treatments always had least degradation. The degradation of mixtures related significantly to not only the volume-weighted mean chemical characteristics but also FDis. Furthermore, the FDis even explained more variation of degradation. The non-additive mixing effects, synergistic effects (faster degradation than predicted) in particular, on degradation of DOM mixtures were rather common, especially in the high- and mid-evenness treatments. Remarkably, the mixing effects increased linearly with the FDis values (r2adj. = 0.426). This study highlights the critical role of functional diversity in regulating degradation of mixed litter-derived DOM. Resulting changes in chemistry and composition of litter leachates due to plant community succession may exert substantial influences on biogeochemical cycling.

Impact of future scenarios of climate change on lignin dynamics in soil: A case study in a Mediterranean savannah.

Lignin is an abundant and recalcitrant biopolymer of major relevance as soil organic matter (SOM) component playing a significant role in its stabilization. In this work, a factorial field experiment was established, where three climatic treatments (W, warming; D, drought; W + D, warming + drought), mimicking future climate change scenarios were installed over five years in a Mediterranean savannah "dehesa", accounting for its landscape diversity (under the tree canopy and in open grassland). A combination of analytical pyrolysis (Py-GC/MS) and the study of biogeochemical proxies based on lignin monomers is used for the direct detection of lignin-derived phenols and to infer possible shifts in lignin dynamics in soil. A total of 27 main lignin-derived methoxyphenols were identified, exhibiting different patterns and proportions, mainly driven by the effect of habitat, hence biomass inputs to SOM. An accelerated decomposition of lignin moieties -(exhibited by higher LG/LS and Al/K + Ac ratios)- is particularly exacerbated by the effect of all climatic treatments. There is also an overall effect on increasing lignin oxidation of side chain in syringyl units, especially under the tree canopy due to the alteration in biomass degradation and potential stimulation of enzyme activities. Conversely, in open grassland these effects are slower since the microbial community is expected to be already adapted to harsher conditions. Our findings suggests that climate change-related temperature and soil moisture deviations impact soil lignin decomposition in dehesas threatening this productive Mediterranean agroecosystem and affecting the mechanism of soil carbon storage.