New insights into membrane fouling in coagulation-ultrafiltration by cake characteristics analysis: A case study with PACl-Al13 and PACl.

Membrane fouling is a bottleneck issue that hindered the further application of ultrafiltration technology. To alleviate membrane fouling, coagulation-ultrafiltration (C-UF) process using polyaluminum chloride (PACl) and PACl-Al13 with high proportion of Al13O4(OH)247+ as coagulants, respectively, were investigated at various pH conditions. Results indicated that an increase in solution pH contributed to larger floc size and looser floc structure for both PACl and PACl-Al13. It was conducive to the formation of more porous cake, as evidenced by mean pore area and pore area distribution of cake, leading to lower reversible fouling. Furthermore, humic acid (HA) removal presented a trend of first increasing and then decreasing with the increase of pH. The optimal HA removal was achieved at pH 6 regardless of coagulant type, suggesting that the slightest irreversible fouling should be occurred at this point. Interestingly, the irreversible fouling with PACl coagulant achieved a minimum value at pH 9, while the minimal irreversible fouling with PACl-Al13 was observed at pH 6. We speculated that the cake formed by PACl could further intercept HA prior to UF process at alkaline pH. Furthermore, compared with PACl, PACl-Al13 had a stronger charge neutralization ability, thus contributing to more compact floc structure and higher HA removal at various pH conditions. By UF fractionation measurement, higher HA removal for PACl-Al13 was due to higher removal of HA with molecular weight less than 50 kDa.

Spatial distribution of sediment dissolved organic matter in oligotrophic lakes and its binding characteristics with Pb(II) and Cu(II).

Dissolved organic matter (DOM), the most active component in interstitial waters, determines the stability of heavy metals and secondary release in sediments. However, little is known about the composition and metal-binding patterns of DOM in interstitial water from oligotrophic lakes affected by different anthropogenic perturbations. Here, 18 interstitial water samples were prepared from sediments in agricultural, residential, tourist, and forest regions in an oligotrophic lake (Shengzhong Lake in Sichuan Province, China) watershed. Interstitial water quality and DOM composition, properties, and Cu(II)- and Pb(II)-binding characteristics were measured via physicochemical analysis, UV-vis spectroscopic, fluorescence excitation-emission matrix-parallel factor analysis (EEM-PARAFAC), and fluorescence titration methods. The DOM, which was produced mainly by microbial activities, had low molecular weights, humification degrees, and aromaticity. Based on EEM-PARAFAC results, the DOM was generally composed of tryptophan- (57.7%), terrestrial humic- (18.7%), microbial humic- (15.6%), and tyrosine-like (8.0%) substances. The DOM in the metal complexes was primarily composed of tryptophan-like substances, which accounted for ~42.6% of the DOM-Cu(II) complexes and ~72.0% of the DOM-Pb(II) complexes; however, microbial humic-like substances primarily contributed to the stability of DOM-Cu(II) (logKCu = 3.7-4.6) and DOM-Pb(II) (logKPb = 4.3-4.8). Water quality parameters did not significantly affect the stability of DOM-metal complexes. We demonstrated that the metal-binding patterns of DOM in interstitial water from oligotrophic lakes are highly dependent on microbial DOM composition and are affected by anthropogenic perturbations to a lesser extent.

Speciation, phytoavailability, and accumulation of toxic elements and sulfur by humic acid-fertilized lemongrass and common sage in a sandy soil treated with heavy oil fly ash: A trial for management of power stations wastes.

Globally, power stations generate huge amounts of the hazardous waste heavy oil fly ash (HOFA), which is rich in Ni, V, Fe, S, and dumped into landfills. Thus, exploring new approaches for a safe recycling and sustainable management of HOFA is needed and of great environmental interest. The potential application of HOFA as an amendment to sandy soils has not been studied yet. This is the first research investigating the potentiality of using HOFA as a soil conditioner. To this end, we conducted a greenhouse experiment in order to investigate the impacts of HOFA addition (1.2, 2.4, 3.6 t ha-1) to sandy soil on the total and available content of nutrients (e.g., S, Fe, Mn, Cu, Zn) and toxic elements (TEs; e.g., Cd, Co, Cr, Ni, Pb, V) in the soil and their phytoextraction and translocation by lemongrass (Cymbopogon citratus) and common sage (Salvia officinalis). We also assessed the impact of humic acid (HA) foliar application (50 and 100 l ha-1) on the growth and elements accumulation by the two plants. The studied HOFA was acidic and highly enriched in S (43,268.0), V (3,527.0), Ni (1774.0), and Fe (15,159.0) (units in mg kg-1). The X-ray absorption near edge structure (XANES) data showed that V in HOFA was composed primarily of V(IV) sorbed onto goethite, V(V) sorbed onto humic substances, in the forms of V2O3, and VCl4. Addition of the lower doses of HOFA (1.2 and 2.4 t ha-1) did not change significantly soil pH, salinity, and the total and available elements content compared to the unamended soil. Although the elements content in the 3.6 t ha-1 HOFA-treated soil was significantly higher than the untreated, the total content of all elements (except for Ni) was lower than the maximum allowable concentrations in soils. HOFA addition, particularly in the highest dose (3.6 t ha-1), decreased significantly the growth and biomass of both plants. Common sage accumulated more elements than lemongrass; however, the elements content in the plants was lower than the critical concentrations for sensitive plants. The foliar application of humic acid enhanced significantly the plant growth and increased their tolerance to the HOFA-induced stress. We conclude that the addition of HOFA up to 2.4 t ha-1 in a single application as amendment to sandy soils is not likely to create any TE toxicity problems to plants, particularly if combined with a foliar application of humic acid; however, repeated additions of HOFA may induce toxicity. These findings should be verified under field conditions.

Seasonal studies of aquatic humic substances from Amazon rivers: characterization and interaction with Cu (II), Fe (II), and Al (III) using EEM-PARAFAC and 2D FTIR correlation analyses.

Aquatic humic substances (AHS) are defined as an important components of organic matter, being composed as small molecules in a supramolecular structure and can interact with metallic ions, thereby altering the bioavailability of these species. To better understand this behavior, AHS were extracted and characterized from Negro River, located near Manaus city and Carú River, that is situated in Itacoatiara city, an area experiencing increasing anthropogenic actions; both were characterized as blackwater rivers. The AHS were characterized by 13C nuclear magnetic ressonance and thermochemolysis GC-MS to obtain structural characteristics. Interaction studies with Cu (II), Al (III), and Fe (III) were investigated using fluorescence spectroscopy applied to parallel factor analysis (PARAFAC) and two-dimensional correlation spectroscopy with Fourier transform infrared spectroscopy (2D-COS FTIR). The AHS from dry season had more aromatic fractions not derived from lignin and had higher content of alkyls moities from microbial sources and vegetal tissues of autochthonous origin, while AHS isolated in the rainy season showed more metals in its molecular architecture, lignin units, and polysacharide structures. The study showed that AHS composition from rainy season were able to interact with Al (III), Fe (III), and Cu (II). Two fluorescent components were identified as responsible for interaction: C1 (blue-shifted) and C2 (red-shifted). C1 showed higher complexation capacities but with lower complexation stability constants (KML ranged from 0.3 to 7.9 × 105) than C2 (KML ranged from 3.1 to 10.0 × 105). 2D-COS FTIR showed that the COO- and C-O in phenolic were the most important functional groups for interaction with studied metallic ions.

Co-adsorption and selective-adsorption of heavy metals and dyes from aqueous solution by bio-based humus/chitosan hydrogels.

An eco-friendly adsorbent was prepared by reverse suspension crosslinking method to remove multiple pollutants from aqueous solution. Both raw materials, derived from humus (HS) and chitosan (CS), are biodegradable and low-cost natural biopolymers. After combining HS with CS, the adsorption capacity was significantly improved due to compensation effects between the two components. HS/CS exhibited the features of amphoteric adsorption through pH adjustment, enabling it to adsorb not only anionic pollutants (Methyl Orange (MO) and Cr(VI)), but also cationic ones (Methylene Blue (MB) and Pb(II)). The adsorption capacities were approximately 242 mg/g, 69 mg/g, 188 mg/g and 57 mg/g for MO, Cr(VI), MB and Pb(II), respectively. HS/CS showed a slight preference for MO in MO/Cr(VI) co-adsorption system, whereas strong selectivity for MB over Pb(II) in MB/Pb(II) system under acidic condition (pH<3.0). This selective behavior would allow for potential applications in separating MB/Pb(II) effluents and selectively recycling Pb(II) in acidic environment. The isothermal and kinetic adsorption behaviors followed Langmuir model and pseudo-second-order model, respectively. The density functional theory (DFT) confirmed that the interaction between metal ions and adsorbents was primarily attributed to chelation and electrostatic adsorption, owing to nitric and oxygenic functional groups. Whereas, the adsorption mechanisms for dyes were involved in electrostatic attraction, H-bond and π-π bond, due to available hydrogen, oxygen, nitrogen atoms and aromatic groups on the surface of adsorbent and adsorbates. The adsorbent could be efficiently regenerated and retained over 90% of its adsorption capacity after five cycles, which has a potential for practical applications in water treatment.

Plastic and terrestrial organic matter degradation by the humic lake microbiome continues throughout the seasons.

Boreal freshwaters go through four seasons, however, studies about the decomposition of terrestrial and plastic compounds often focus only on summer. We compared microbial decomposition of 13C-polyethylene, 13C-polystyrene, and 13C-plant litter (Typha latifolia) by determining the biochemical fate of the substrate carbon and identified the microbial decomposer taxa in humic lake waters in four seasons. For the first time, the annual decomposition rate including separated seasonal variation was calculated for microplastics and plant litter in the freshwater system. Polyethylene decomposition was not detected, whereas polystyrene and plant litter were degraded in all seasons. In winter, decomposition rates of polystyrene and plant litter were fivefold and fourfold slower than in summer, respectively. Carbon from each substrate was mainly respired in all seasons. Plant litter was utilized efficiently by various microbial groups, whereas polystyrene decomposition was limited to Alpha- and Gammaproteobacteria. The decomposition was not restricted only to the growth season, highlighting that the decomposition of both labile organic matter and extremely recalcitrant microplastics continues throughout the seasons.

Mitigation of drought stress in maize and sorghum by humic acid: differential growth and physiological responses.

BACKGROUND: Drought is a major determinant for growth and productivity of all crops, including cereals, and the drought-induced detrimental effects are anticipated to jeopardize world food security under the ongoing global warming scenario. Biostimulants such as humic acid (HA) can improve drought tolerance in many cereals, including maize and sorghum. These two plant species are genetically related; however, maize is more susceptible to drought than sorghum. The physiological and biochemical mechanisms underlying such differential responses to water shortage in the absence and presence of HA, particularly under field conditions, are not fully understood. RESULTS: Herein, the effects of priming maize and sorghum seeds in 100 mg L-1 HA on their vegetative growth and physiological responses under increased levels of drought (100%, 80%, and 60% field capacity) were simultaneously monitored in the field. In the absence of HA, drought caused 37.0 and 58.7% reductions in biomass accumulation in maize compared to 21.2 and 32.3% in sorghum under low and high drought levels, respectively. These responses were associated with differential retardation in overall growth, relative water content (RWC), photosynthetic pigments and CO2 assimilation in both plants. In contrast, drought increased root traits as well as H2O2, malondialdehyde, and electrolyte leakage in both species. HA treatment significantly improved the growth of both plant species under well-watered and drought conditions, with maize being more responsive than sorghum. HA induced a 29.2% increase in the photosynthetic assimilation rate in maize compared to 15.0% in sorghum under high drought level. The HA-promotive effects were also associated with higher total chlorophyll, stomatal conductance, RWC, sucrose, total soluble sugars, total carbohydrates, proline, and total soluble proteins. HA also reduced the drought-induced oxidative stress via induction of non-enzymic and enzymic antioxidants at significantly different extents in maize and sorghum. CONCLUSION: The current results identify significant quantitative differences in a set of critical physiological biomarkers underlying the differential responses of field-grown maize and sorghum plants against drought. They also reveal the potential of HA priming as a drought-alleviating biostimulant and as an effective approach for sustainable maize and sorghum production and possibly other crops in drought-affected lands.

Assessing sorption of fluoroquinolone antibiotics in soils from a Kd compilation based on pure organic and mineral components.

The presence of fluoroquinolone (FQ) antibiotics in soils may cause a threat to human health due to overexposure and the generation of antibiotic resistance genes. Understanding their sorption behavior in soils is important to predict subsequent FQ (bio) availability. Here, FQ sorption in pure soil organic (i.e., humic substances) and mineral (i.e., metal oxides; phyllosilicates) components is evaluated through a solid-liquid distribution coefficient (Kd (FQ)) dataset consisting of 243 entries originated from 80 different studies, to elucidate their respective contribution to the overall Kd (FQ) in bulk soils. First, different factors affecting FQ sorption and desorption in each of these soil phases are critically discussed. The strong role of pH in Kd (FQ), due to the simultaneous effect on both FQ speciation and surface charge changes, encouraged the derivation of normalized sorption coefficients for the cationic, zwitterionic and anionic FQ species in humic substances and in different phyllosilicates. Kd (FQ) in metal oxides revealed a key role of metal nature and material specific surface area due to complexation sorption mechanisms at neutral pH. Cumulative distribution functions (CDF) were applied to each dataset to establish a sorption affinity range for each phase and to derive best estimate Kd (FQ) values for those materials where normalized sorption coefficients to FQ species were unavailable. The data analysis conducted in the different soil phases set the basis for a Kd (FQ) prediction model, which combined the respective sorption affinity of each phase for FQ and phase abundance in soil to estimate Kd (FQ) in bulk soils. The model was subsequently validated with sorption data in well characterized soils compiled from the literature.

Nano bio fertilizer capsules for sustainable agriculture.

A novel nano bio-fertilizer encapsulation method was developed to crosslink chitosan and alginate with humic acid. These nanocapsules, referred to as (Ch./Alg.HA.NPK) or (Ch./Alg.HA.NPK.PGPRs), were loaded with nanoscale essential agro-nutrients (NPK) and beneficial microorganisms Pseudomonas Fluorescence abbreviated as (P.Fluorescence). Structural and morphological analyses were conducted using FourierTransform Infrared, Thermogravimetric Analysis, Scanning Electron Microscopy, Malvern Zeta NanoSizer, and Zeta potential. Encapsulation efficiency and water retention were also determined compared to control non-crosslinked nanocapsules. The sustained cumulative release of NPK over 30 days was also investigated to 33.2%, 47.8%, and 68.3%, alternatively. The release mechanism, also assessed through the kinetic module of the Korsemeyer- Peppas Mathematical model, demonstrated superior performance compared to non-crosslinked nanocapsules (chitosan/alginate). These results show the potential of the synthesized nanocapsules for environmentally conscious controlled release of NPK and PGPRs, thereby mitigating environmental impact, enhancing plant growth, and reducing reliance on conventional agrochemical fertilizers.

Transcriptome analysis reveals the humic acids and chitosan suppressing Alternaria solani growth.

AIMS: Understanding the inhibitory effects of natural organic substances on soil-borne pathogenic fungi and the relevant molecular mechanisms are highly important for future development of green prevention and control technology against soil-borne diseases. Our study elucidates the inhibitory effect of the combined application of humic acids (HAs) and chitosan on Alternariasolani and the light on the corresponding mechanism. METHODS AND RESULTS: The effect on A. solani growth by HAs incorporated with chitosan was investigated by plate culture and the corresponding mechanism was revealed using transcriptomics. The colony growth of A. solani was suppressed with the highest inhibition rate 33.33% when swine manure HAs was compounded with chitosan at a ratio of 1:4. Chitosan changed the colony morphology from round to irregularly. RNA-seq in the HAs and chitosan (HC) treatment revealed 239 differentially expressed genes compared with the control. The unigenes associated with enzymes activities related to growth and biological processes closely related to mycelial growth and metabolism were downregulated. RNA-seq also revealed that chitosan altered the expression of genes related to secondary metabolism, fungal cell wall formation and polysaccharide synthesis, and metabolism. Meanwhile, weighted gene co-expression network analysis showed that, genes expression in the module positively correlated with mycelial growth was significantly reduced in the HC treatment; and the results were verified by real-time quantitative polymerase chain reaction. CONCLUSIONS: The co-inhibition effect of HAs and chitosan on A. solani is associated with downregulated genes expression correlated with mycelial growth.

Photo-transformation of ofloxacin in natural aquatic conditions: Impact of indirect photolysis on the product profile and transformation mechanism.

The natural phototransformation of organic pollutants in the environment depends on several water constituents, including inorganic ions, humic substances, and pH. However, the literature information concerning the influence of various water components on the amount of phototransformation and their impact on the development of various transformation products (TPs) is minimal. This study investigated the phototransformation of ofloxacin (OFL), a fluoroquinolone antibiotic, in the presence of various water components such as cations (K+, Na+, Ca2+, NH4+, Mg2+), anions (NO3-, SO42-, HCO3-, CO32-, PO43-), pH, and humic substances when exposed to natural sunlight. The study reveals that neutral pH levels (0.39374 min⁻1) enhance the phototransformation of OFL in aquatic environments. Carbonate, among anions, shows the highest rate constant (2.89966 min⁻1), significantly influencing OFL phototransformation, while all anions exhibit a notable impact. In aquatic environments, indirect phototransformation of OFL, driven by increased reactive oxygen species, expedites light-induced reactions, potentially enhancing OFL phototransformation. A clear difference was visible in the type of transformation products (TPs) formed during direct and indirect photolysis. The impact of indirect photolysis in the product profile was evaluated by examining the unique properties of TPs in direct and indirect photolysis. The primary transformation products were generated by oxidation and cleavage processes directed towards the ofloxacin piperazinyl, oxazine, and carboxyl groups. The toxicity assessment of TPs derived from OFL revealed that among the 26 identified TPs, TP3 (demethylated product), TP7 and TP8 (decarboxylated products), and TP15 (piperazine ring cleaved product) could potentially have some toxicological effects. These findings suggest that the phototransformation of OFL in the presence of various water components is necessary when assessing this antibiotic's environmental fate.

Removal of trivalent chromium ions in model contaminated groundwater using hexagonal boron nitride as an adsorbent.

The feasibility of using hexagonal boron nitride (h-BN) to treat heavy metal Cr(III) from model contaminated groundwater was evaluated in this study by adsorption experiments and characterizations. To the best of our knowledge, this study is the first attempt to conduct the adsorption of Cr(III) by h-BN under various experimental conditions such as exposure time, ratio of adsorbates and adsorbents, solution pH, background ions with different ionic strength, and the presence of humic acids (HA) in model contaminated groundwater. The optimized h-BN showed excellent maximum adsorption capacity (i.e., 177 mg ∙ g-1) when the concentrations of Cr(III) and h-BN were 10 and 10 mg ∙ L-1, respectively. Subsequently, we confirmed there was a negligible change in the adsorption performance of Cr(III) by h-BN in the presence of co-ions (i.e., K and Mg) in concentrations in a range from 50 to 1000 mg ∙ L-1. Furthermore, the adsorption performance of Cr(III) gradually improved with HA concentrations from 2.5 to 25 mg ∙ L-1. Interestingly, the maximum adsorption performance of Cr(III) by both HA and h-BN increased until 500 mg ∙ g-1 in the presence of 25 mg ∙ L-1 HA. The adsorption mechanism was clarified by Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. Additionally, we successfully confirmed that h-BN could be reused until five cycles. On the basis of the adsorption performance results and characterizations, h-BN can be utilized as an efficient and practical adsorbent to treat Cr(III) in groundwater treatment.

Interactions between organic matter and alkaline minerals in bauxite residue: implication for soil restoration.

Ecological restoration of bauxite residue has received extensive attention, and organic matter plays a crucial role in the soil formation process of bauxite residue. However, the interaction between organic matter and alkaline minerals in bauxite residue is not well understood. In this work, molecular spectroscopic techniques combined with isothermal titration calorimetry (ITC) were employed to investigate the interactions between humic acid (HA) and four representative alkaline minerals in bauxite residue (calcite, garnet, sodalite, and cancrinite). The results show that the adsorption processes of HA onto calcite and garnet were primarily governed by monolayer surface adsorption and controlled by surface reactions, which were different for sodalite and cancrinite. Both garnet and cancrinite had strong binding affinities with fluorescent HA, while cancrinite only bound with a small fraction of HA. In contrast, the bindings of calcite and sodalite with fluorescent HA were weak. The ITC results indicate distinct thermodynamic properties of different alkaline minerals in the interaction with HA. The molar enthalpy of calcite was - 45.88 kJ/mol, which was much higher than those of garnet, sodalite, and cancrinite, suggesting that calcite exhibited a relatively uniform interaction mechanism with HA dominated by enthalpy change, while the others showed heterogeneous entropy-driven mechanisms. The findings contribute to a better understanding on the microscale connections between organic matter and alkaline minerals in bauxite residue.

Characterization and spatiotemporal variations of fluorescent dissolved organic matter in leachate from old landfill-derived incineration residues and incombustible waste.

Dissolved organic matter (DOM) influences the bioavailability and behavior of trace metals and other pollutants in landfill leachate. This research characterized fluorescent dissolved organic matter (FDOM) in leachate from an old landfill in Japan during a 13-month investigation. We employed excitation-emission matrix (EEM) fluorescence spectroscopy with parallel factor analysis (PARAFAC) to deconvolute the FDOM complex mixture into three fluorophores: microbial humic-like (C1), terrestrial humic-like (C2), and tryptophan-like fluorophores (C3). These FDOM components were compared with findings from other studies of leachate in landfills with different waste compositions. The correlations among EEM-PARAFAC components, dissolved organic carbon (DOC) concentration, and ultraviolet-visible and fluorescence indices were evaluated. The FDOM in leachate varied spatially among old and extended leachate collected in the landfill and leachate treatment facility. The FDOM changed temporally and decreased markedly in August 2019, November 2019, and April 2020. The strong positive correlation between HIX and %C2 (r = 0.87, ρ = 0.91, p < 0.001)) implies that HIX may indicate the relative contribution of terrestrial humic-like components in landfill leachate. The Fmax of C1, C2, and C3 and the DOC concentration showed strong correlations among each other (r > 0.72, ρ > 0.78, p < 0.001) and positive correlations with leachate level (r > 0.41, p < 0.001), suggesting the importance of hydrological effects and leachate pump operation on FDOM.

Effect of interactions between humic acid and cerium oxide nanoparticles on the toxicity to the Chlorella sp.

With the wide application of nanomaterials, the concentration of nanomaterials in natural water continues to increase, which poses a severe threat to the water environment. However, the influence of organic matter and nanomaterials rich in natural water on the toxic effect of algae growth is still unclear. In this study, the effects of humic acid (HA) and nano-cerium oxide (nCeO2) on the physiology and transcriptome of Chlorella sp. were analyzed, and the mechanism of the toxic effect of HA on Chlorella sp. under nCeO2 stress was revealed. Under 20-200 mg/L nCeO2 stress, the growth of Chlorella cells was inhibited and the highest inhibition rate reached 52% within 200 mg/L nCeO2. The Fv/Fm and ETRmax values of Chlorella sp. decreased from 0.490 and 24.45 (20 mg/L nCeO2) to 0.488 and 23.4 (100 mg/L nCeO2), respectively. Under the stimulation of nCeO2, the level of reactive oxygen species in algal cells was increased, accompanied by lipid peroxidation and membrane damage. However, the addition of HA at concentrations of 5-10 mg/L effectively alleviated the toxic effect of nCeO2 on Chlorella sp. Transcriptome analysis showed that 10 mg/L HA could alleviate the cellular stress at 100 mg/L nCeO2 on Chlorella sp. by regulating genes related to photosynthesis and metabolism pathways. Moreover, the downregulation of genes (e.g., Lhca1, Lhcb1, AOC3, and AOC2) indicated that HA reduced the level of oxidative stress in Chlorella sp. These findings offer novel insights of evaluating the ecotoxicity nCeO2 and HA in natural water environment and their impact on Chlorella sp.

Dynamic changes in dissolved organic matter during transport of landfill leachate in porous medium.

The dynamic changes in dissolved organic matter (DOM) during the transport of landfill leachate (LL) in porous medium should be explored, considering the high levels of DOM in the LL of municipal solid waste. Column experiments were carried out at 25 °C at a Darcy's flux of 0.29 cm/h for 2722 h to compare the transport of Cl-, ultraviolet absorbance at 254 nm (UV254), chemical oxygen demand (COD), and dissolved organic carbon (DOC) in the simulated porous medium by using the CXTFIT2.1 code. Results showed that the convection-dispersion equation (CDE) could describe Cl- transport well. The high levels of λ and D could be highly correlated with the physicochemical properties of the porous medium. The transport of the studied DOM with evident aromatic character could be described appropriately by the CDE model with the first-order reaction assumption, considering the similar variation trends of UV254, COD, and DOC in the effluent during experiments. Specifically, the values of retardation factor (R) were in the following order: DOC > UV254 > COD, whereas the low values of the first-order decay coefficient (k1) for DOC and COD were still higher than that for UV254. High contents of humic-like substances in the DOM with complex toxic components resulted in the natural low removal efficiencies of COD, DOC, and UV254 (≤ 23%), which could be confirmed by the variations of fluorescence index (FI) and humification index (HIX) in the effluent. The results should be helpful in evaluating the environmental risk induced by the LL leakage in a landfill site.

Inhibit or promote? Trade-off effect of dissolved organic matter on the laccase-mediator system.

A biocatalytic system comprising fungal laccase and mediators can generate phenol radicals and efficiently eliminate various triarylmethane dyes. This study systematically explores the kinetic impact of dissolved organic matter (DOM), represented by humic substance (HS consisting of 90% fulvic acid, from lignite), on the decolorization of seven typical triarylmethane dyes by Trametes versicolor laccase and twenty natural mediators. Among these, 4-hydroxybenzyl alcohol (4-HA) and methyl violet (MV) undergo in-depth investigation regarding degradation products, pathways, and reaction mechanisms. In instances where HS hampers laccase-alone decolorization, such as malachite green, Coomassie brilliant blue, bromophenol blue, and acid magenta, this inhibition may persist despite mediator introduction. Conversely, in cases where HS facilitates decolorization, such as crystalline violet and ethyl violet, most laccase-mediator systems (LMSs) can still benefit. For MV decolorization by laccase and 4-HA, HS's kinetic effect is controlled by concentration and reaction time. A 5 mg/L HS increased the decolorization rate from 50% to 67% within the first hour, whereas 10 mg/L HS only achieved 45%. After 16 h of reaction, HS's impact on decolorization rate diminishes. Furthermore, the addition of HS enhances precipitation production, probably due to its involvement in polymerization with MV and mediator. Computational simulations and spectral monitoring reveal that low HS concentrations accelerate laccase-mediated demethylation by disrupting the chromophores bound to MV, thus promoting the decolorization of MV. Conversely, inhibition by high HS concentrations stems from the competitive binding of the enzyme pocket to the mediator, and the reduction of phenol free radicals in the system. Molecular docking and kinetic simulations revealed that laccase forms complexes with both the mediator and MV. Interestingly, the decolorization of MV occurred through a non-radical mechanism in the presence of HS. This work provided a reference for screening of high catalytic performance mediators to remove triarylmethane dyes in the actual water environment.

Humic Acid-Functionalized Lignin-Based Coatings Regulate Nutrient Release and Promote Wheat Productivity and Grain Quality.

The rational application of fertilizers is crucial for achieving high crop yields and ensuring global food security. The use of biopolymers for slow-release fertilizers (SRFs) development has emerged as a game-changer and environmentally sustainable pathway to enhance crop yields by optimizing plant growth phases. Herein, with a renewed focus on circular bioeconomy, a novel functionalized lignin-based coating material (FLGe) was developed for the sustained release of nutrients. This innovative approach involved the extraction and sustainable functionalization of lignin through a solvent-free esterification reaction with humic acid─an organic compound widely recognized for its biostimulant properties in agriculture. The primary objective was to fortify the hydration barrier of lignin by reducing the number of its free hydroxyl groups, thereby enhancing release control, while simultaneously harnessing the agronomic benefits offered by humic acid. After confirming the synthesis of functionalized lignin (FLGe) through 13C NMR analysis, it was integrated at varying proportions into either a cellulosic or starch matrix. This resulted in the creation of five distinct formulations, which were then utilized as coatings for diammonium phosphate (DAP) fertilizer. Experimental findings revealed an improved morphology and hardness (almost 3-fold) of DAP fertilizer granules after coating along with a positive impact on the soil's water retention capacity (7%). Nutrient leaching in soil was monitored for 100 days and a substantial reduction of nutrients leaching up to 80% was successfully achieved using coated DAP fertilizer. Furthermore, to get a fuller picture of their efficiency, a pot trial was performed using two different soil textures and demonstrated that the application of FLGe-based SRFs significantly enhanced the physiological and agronomic parameters of wheat, including leaf evolution and root architecture, resulting in an almost 50% increase in grain yield and improved quality. The results proved the potential of lignin functionalization to advance agricultural sustainability and foster a robust bioeconomy aligning with the premise "from the soil to the soil".

Synthesis and evaluation of a novel cross-linked biochar/ferric chloride hybrid material for integrated coagulation and adsorption of turbidity and humic acid from synthetic wastewater: Implications for sludge valorisation.

The deep removal of organic pollutants is challenging for coagulation technology in drinking water and wastewater treatment plants to satisfy the rising water standards. Iron (III) chloride (FeCl3) is a popular inorganic coagulant; although it has good performance in removing the turbidity (TB) in water at an alkaline medium, it cannot remove dissolved pollutants and natural organic matter such as humic acid water solution. Additionally, its hygroscopic nature complicates determining the optimal dosage for effective coagulation. Biochar (BC), a popular adsorbent with abundant functional groups, porous structure, and relatively high surface area, can adsorb adsorbates from water matrices. Therefore, combining BC with FeCl3 presents a potential solution to address the challenges associated with iron chloride. Consequently, this study focused on preparing and characterizing a novel biochar/ferric chloride-based coagulant (BC-FeCl3) for efficient removal of turbidity (TB) and natural organic matter, specifically humic acid (HA), from synthetic wastewater. The potential solution for the disposal of produced sludge was achieved by its recovering and recycling, then used in adsorption of HA from aqueous solution. The novel coagulant presented high TB and HA removal within 10 min of settling period at pH solution of 7.5. Furthermore, the recovered sludge presented a good performance in the adsorption of HA from aqueous solution. Adsorption isotherm and kinetics studies revealed that the Pseudo-second-order model best described kinetic adsorption, while the Freundlich model dominated the adsorption isotherm.

Revealing mechanism of phenol-amine reaction to form humus in compost based on high-resolution liquid chromatography mass spectrometry and spectroscopy.

Humus is the stable form of carbon storage in straw compost. The phenol-amine reaction is a pathway for humus formation in straw compost. In this study, two reaction systems, GP group (pyrogallol and glycine) and GCP group (catechol, pyrogallol, and glycine), were constructed in a simulated composting environment and revealed the molecular binding mechanism of the phenol-amine reaction through spectroscopy and mass spectrometry. The results showed that phenolic self-polymerization was faster than phenol-amine reaction. Therefore, the aromatization degree of GP was 27.14 % higher than that of GCP. The phenol-amine reaction first produced fulvic acid, and then formed humus units rich in active functional group structures (i.e., phenolic hydroxyl and carboxyl groups). These units further captured small molecule compounds to form humic acid eventually. This study would provide theoretical support for exploring the humus formation process and the promotion of straw humification by adding phenol or amino acids to compost.