Unraveling how Fe-Mn modified biochar mitigates sulfamonomethoxine in soil water: The activated biodegradation and hydroxyl radicals formation.

This study indicated that the application of a novel Fe-Mn modified rice straw biochar (Fe/Mn-RS) as soil amendment facilitated the removal of sulfamonomethoxine (SMM) in soil water microcosms, primarily via activating degradation mechanism rather than adsorption. The similar enhancement on SMM removal did not occur using rice straw biochar (RS). Comparison of Fe/Mn-RS with RS showed that Fe/Mn-RS gains new physic-chemical properties such as abundant oxygenated C-centered persistent free radicals (PFRs). In the Fe/Mn-RS microcosms, the degradation contributed 79.5-83.8% of the total SMM removal, which was 1.28-1.70 times higher than that in the RS microcosms. Incubation experiments using sterilized and non-sterilized microcosms further revealed that Fe/Mn-RS triggered both the biodegradation and abiotic degradation of SMM. For abiotic degradation of SMM, the abundant •OH generation, induced by Fe/Mn-RS, was demonstrated to be the major contributor, according to EPR spectroscopy and free radical quenching experiments. Fenton-like bio-reaction occurred in this process where Fe (Ⅲ), Mn (Ⅲ) and Mn (Ⅳ) gained electrons, resulting in oxidative hydroxylation of SMM. This work provides new insights into the impacts of biochar on the fates of antibiotics in soil water and a potential solution for preventing antibiotic residues in agricultural soil becoming a non-point source pollutant.

Regulation and role of extracellular polymeric substances in the defensive responses of Dictyosphaerium sp. to enrofloxacin stress.

Algae are susceptible to enrofloxacin (ENR), an antibiotic frequently detected in aquatic environments. However, algal responses, especially the secretion and roles of extracellular polymeric substances (EPS), under ENR exposure remain unknown. This study is the first to elucidate the variation in algal EPS triggered by ENR at both the physiological and molecular levels. The results showed that EPS were significantly (P < 0.05) overproduced along with increased polysaccharide and protein contents in algae exposed to 0.05, 0.5, and 5 mg/L ENR. Secretion of aromatic proteins, especially tryptophan-like substances with more functional groups or aromatic rings, was specifically stimulated. Furthermore, the genes with upregulated expression related to carbon fixation, aromatic protein biosynthesis, and carbohydrate metabolism are direct causes of enhanced EPS secretion. Improved EPS levels increased the cell surface hydrophobicity and provided more adsorption sites for ENR, which strengthened the van der Waals interaction and reduced ENR internalization. The hormesis effects of ENR were alleviated, as illustrated by the less affected cell density, chlorophyll a/b, and carotenoids biosynthesis in algae with EPS. These findings demonstrate the involvement of EPS in algal ENR resistance and promote a deeper understanding of the ecological effects of ENR in aquatic environments.

Biodegradation of sulfametoxydiazine by Alcaligenes aquatillis FA: Performance, degradation pathways, and mechanisms.

This study reports the isolation and characterization of a novel bacterial strain Alcaligenes aquatillis FA with the ability to degrade sulfametoxydiazine (SMD), a commonly used sulfonamide antibiotic (SA) in livestock and poultry production. The biodegradation kinetics, pathways, and genomic background of SMD by FA were investigated. The results showed that strain FA had high specificity to degrade SMD, and was unable to effectively degrade its isomer, sulfamonomethoxine. The SMD biodegradation followed a first-order kinetic model with a rate constant of 27.39 mg·L-1·day-1 and a half-life of 5.98 days. The biodegradation pathways and detoxification processes of SMD were proposed based on the identification of its biodegradation byproducts and the biotoxicity assessment using both the ecological structure-activity relationship (ECOSAR) model and biological indicator. The involvement of novel degrading enzymes, such as dimethyllsulfone monooxygenase, 4-carboxymuconolactone decarboxylase, and 1,4-benzoquinone reductase, was inferred in the SMD biodegradation process. The presence of sul2 and dfrA genes in strain FA, which were constitutively expressed in its cells, suggests that multiple mechanisms were employed by the strain to resist SMD. This study provides new insights into the biodegradation of sulfonamide antibiotics (SAs) as it is the first to describe an SMD-degrading bacterium and its genetic information.

[Effect of Antibiotic-Degrading Bacteria on Maturity and Bacterial Community Succession During Pig Manure Composting].

The inoculation of antibiotic-degrading bacteria into manure could promote the removal of antibiotics during composting. However, knowledge on the impact of inoculating these antibiotic-degrading bacteria on the composting process and indigenous microbial community succession is still limited. This study assessed the antibiotic removal efficiency in pig manure after inoculating a microbial inoculum with antibiotic-degrading bacteria as the key component. The effect of inoculating this microbial inoculum on the physicochemical dynamics and the succession of the manure bacterial community during composting was also analyzed. The results showed that the antibiotic degradation in pig manure reached 81.95% after inoculating the microbial inoculum. When compared with that in the control, the total concentration of antibiotic residues in manure with the microbial agent inoculated was decreased by 42.18%. During composting, inoculating the microbial inoculum accelerated the temperature rise of compost, favored water loss, and alleviated the release of NH3 and H2S. Moreover, the total nutrient content (nitrogen, phosphorus, and potassium) in the final compost and the germination index of radish seeds increased by 6.80% and 68.33%, respectively, after inoculating this microbial inoculum. Furthermore, inoculating the microbial inoculum increased the content of stable organic carbon in the final compost and decreased the content of recalcitrant substances such as cellulose and hemicellulose. The analysis of the manure bacterial community showed that inoculating the microbial inoculum increased the relative abundances of Actinomycetes and Firmicutes in the compost. In particular, the thermophilic bacteria that was positively related to the compost temperature was increased significantly (P<0.01) after inoculating the microbial inoculum, whereas the relative abundance of pathogenic bacteria was correspondingly decreased. Network analysis of the bacterial coexistence pattern showed that inoculating this microbial inoculum also changed the interaction pattern of indigenous manure bacterial communities, which greatly reduced the complexity and connectivity of the bacterial interaction and improved the ecological relationship between beneficial bacteria and other bacterial communities. The effect of this microbial inoculum on the interaction with manure bacterial community laid a foundation for the establishment of a new and healthier composting bacterial community. This study provides a scientific basis for the application and development of multifunctional antibiotic-degrading microbial agents in manure treatments.

High-Energy-Density Organic Amendments Enhance Soil Health.

Soil microbial biomass (SMB) and soil microbial communities (SMCs) are the key factors in soil health and agricultural sustainability. We hypothesized that low bioavailable carbon (C) and energy were the key limiting factors influencing soil microbial growth and developed a new fertilization system to address this: the simultaneous application of mineral fertilizers and high-energy-density organic amendments (HED-OAs). A microcosm soil incubation experiment and a Brassica rapa subsp. chinensis pot culture experiment were used to test the effects of this new system. Compared to mineral fertilizer application alone, the simultaneous input of fertilizers and vegetable oil (SIFVO) achieved a bacterial abundance, fungal abundance, and fungal:bacterial ratio that were two orders of magnitude higher, significantly higher organic C and nitrogen (N) content, significantly lower N loss, and nearly net-zero N2O emissions. We proposed an energy and nutrient threshold theory to explain the observed bacterial and fungal growth characteristics, challenging the previously established C:N ratio determination theory. Furthermore, SIFVO led to microbial community improvements (an increased fungal:bacterial ratio, enriched rhizosphere bacteria and fungi, and reduced N-transformation bacteria) that were beneficial for agricultural sustainability. A low vegetable oil rate (5 g/kg) significantly promoted Brassica rapa subsp. chinensis growth and decreased the shoot N content by 35%, while a high rate caused severe N deficiency and significantly inhibited growth of the crop, confirming the exceptionally high microbial abundance and indicating severe microbe-crop competition for nutrients in the soil.

Toxicity alleviation and metabolism enhancement of nonylphenol in green algae Dictyosphaerium sp. by NaHCO3.

Nonylphenol (NP) toxicity limits the improvements in its algal remediation efficiency. This study comprehensively investigated the performance and mechanism of NaHCO3-driving effects on NP-exposed algae. The results showed that NaHCO3 enhanced algal resistance to NP and the corresponding EC50 values increased 1.31-4.25 times. Further, the toxicological effects of NP reduced with increasing pyrenoid volume and chlorophyll and carotenoids production, and decreasing cellular damage degree. Moreover, the concentration of extracellular polymeric substances was enhanced and more NP adsorption sites were formed. Consistently, RNA-seq demonstrated significant expression alterations in genes related to energy metabolism, cellular synthesis, photosynthesis, and carbon fixation. Besides, NP biodegradation rate was increased by 15.2 % and 11.1 % in the 1, and 4 mg/L NP treatments, respectively. Identification of degradation intermediates and their toxicity via Ecological Structure Activity Relationship program showed that NaHCO3 accelerated sequential α-C removal from NP in algae with faster generation of less toxic metabolites, namely, 4-ethylphenol, 4-cresol and 4-hydroxybenzoic acid. This study provides new insights into the role of NaHCO3 in toxicity alleviation and metabolism enhancement of NP in algae and can assist NP bioremediation efforts in aquatic environment.

Copper exposure effects on antibiotic degradation in swine manure vary between mesophilic and thermophilic conditions.

Antibiotic and heavy metal commonly coexist in manure. This study investigated the effect of Cu exposure on antibiotic dissipation in swine manure under two typical temperature (mesophilic and thermophilic) conditions in composting, focusing on biodegradation behaviors. The results showed that Cu promoted the dissipation of norfloxacin and sulfamethazine (SMZ) in solid swine manure under mesophilic conditions at initial concentrations ranging from 407.8 to 1353.0 mg·kg-1 but insignificantly influenced or even inhibited their dissipation under thermophilic conditions. A liquid manure suspension culture experiment was designed to elucidate the response of SMZ biodegradation to Cu. In this manure suspension, biodegradation was the major mechanism for SMZ removal, but SMZ biodegradation was decreased from 23.2 % to 5.5 % when the Cu concentration increased from 0 to 10 mg L-1. Mesophilic and heat-resistant SMZ-degrading bacterial inoculants were subsequently prepared using 21 SMZ-degrading bacteria that were isolated and identified from manure suspension cultures. Inoculating both mesophilic and heat-resistant SMZ-degrading bacterial inoculants enhanced SMZ degradation in sterilized manure suspensions without Cu addition, however only mesophilic SMZ-degrading inoculum improved SMZ degradation after Cu addition. In the presence of Cu, the heat-resistant SMZ-degrading inoculum failed to enhance SMZ removal in manure suspensions. Our findings can help to answer why Cu has varied effects on antibiotic degradation during manure composting.

Nanoscale zero-valent iron alters physiological, biochemical, and transcriptomic response of nonylphenol-exposed algae (Dictyosphaerium sp.).

Nanoparticles and organic pollutants are two major contaminants found in aquatic environments. Algae are regarded as the model organism for the risk assessment of pollutants in water. In our previous study, we investigated the toxic effects of nonylphenol (NP), a typical organic water pollutant, on algae; however, it remains unclear how algae respond to the coexistence of NP and nanoparticles. In this study, a concentration gradient of nanoscale zero-valent iron (nZVI; 10, 50, 100, and 200 mg/L) was added to NP-exposed Dictyosphaerium sp. to investigate both the toxic effects of this combination and the potential for NP removal. nZVI had a dose-dependent effect on NP-exposed algae, with high nZVI concentrations significantly decreasing algal biomass and pigment content, as well as severely damaging algal cellular ultrastructure. In addition, genes involved in antioxidant response, photosynthesis, and ribosome synthesis were significantly altered when NP-exposed algae were incubated with nZVI. In contrast to high nZVI concentrations, adding a small concentration of nZVI led to reduced toxicity in NP-exposed algae, while significantly enhancing the NP removal rate. This study improves our understanding of algal responses to various pollutants and suggests that nZVI may assist in the remediation of NP in aquatic ecosystems.

Physiological and transcriptional responses of Dictyosphaerium sp. under co-exposure of a typical microplastic and nonylphenol.

Microplastics (MPs) and nonylphenol (NP) are typical pollutants that are frequently detected in aquatic environments and can pose a risk to aquatic organisms. However, the responses of algae, the producers in aquatic ecosystems, to MP and NP co-exposure have not been extensively investigated. In this study, polystyrene (PS, 50 mg/L) was selected as a representative MP to evaluate its short-term effects on algae treated with NP (4 mg/L). The results showed that PS mitigated the toxicity of NP to algae after 96 h of exposure, as illustrated by the higher cell densities and pigment concentrations, as well as lower extracellular protein contents and better integrity of intracellular structures, in algae subjected to PS + NP treatment compared with those subjected to NP treatment. Moreover, the upregulated expression of genes involved in photosynthesis and downregulated expression of ribosomal genes as well as genes encoding ATPase and antioxidase, analyzed through RNA-sequencing analysis, further indicated the potential repair and defense mechanisms of PS in NP-treated algae.

Effects of Fe2O3 nanoparticles on extracellular polymeric substances and nonylphenol degradation in river sediment.

In this study, the impact of Fe2O3 nanoparticles (nFe2O3) on microbial extracellular polymeric substances (EPS) and nonylphenol (NP) degradation in sediment were investigated. The results showed that the addition of nFe2O3 lowered the degree of EPS overproduction and the amount of polysaccharides and proteins secreted in NP contaminated sediment. Particularly, the secretion of colloidal EPS (C-EPS) lowered significantly (P < 0.05), and the content of tyrosine-like, tryptophan-like, and soluble microbial by-product-like substances in C-EPS also decreased, leading to a lower aromaticity, humification, and hydrophobicity of C-EPS. Furthermore, with lower C-EPS content in water, NP was adsorbed to sediment more easily, and the weakened toxic effect of NP to bacteria as well as a higher proportion of organic matter degrading microbes stimulated NP degradation. These findings revealed the vital role of nFe2O3 in alleviating NP toxicity to microbes and reducing NP ecological risk in aquatic environments.

Interactions of iron-based nanoparticles with soil dissolved organic matter: adsorption, aging, and effects on hexavalent chromium removal.

The interactions and mechanisms between soil dissolved organic matter (DOM) and three types of iron-based nanoparticles (NPs), i.e., nanoscale zero-valent iron (nZVI) particles, Fe2O3 NPs, and Fe3O4 NPs, were investigated in short-term exposure experiments. The adsorption results showed that soil DOM was rapidly adsorbed on the surface of the iron-based NPs with the adsorption rate varying according to Fe3O4 > Fe2O3 > nZVI. Spectral analysis results revealed that aromatic DOM fractions with high-molecular-weights were preferentially adsorbed. The binding mechanism was determined as hydrogen bonding and ligand exchange via Fourier transform infrared spectroscopy (FT-IR) analysis. Scanning electron microscopy, FT-IR, X-ray photoelectron spectroscopy, and X-ray diffraction were used to identify the corrosion products of the three iron-based NPs at the adsorption equilibrium. The results suggest that Fe3O4 and/or γ-Fe2O3 and α-FeOOH were the main corrosion products of nZVIs and α-FeOOH was obtained as an aged product of Fe3O4 NPs. Results of Cr(VI) removal tests suggest that the aged nZVI achieved 79.87% of Cr(VI) removal and the Cr(VI) removal efficiency was significantly improved by coating DOM onto Fe2O3 NPs. The overall data indicate the fate and transformation of iron-based NPs and the enhancement for Cr(VI) removal after interactions between DOM and NPs.

Enhanced excretion of extracellular polymeric substances associated with nonylphenol tolerance in Dictyosphaerium sp.

Dictyosphaerium sp. is tolerant to nonylphenol (NP); however, knowledge regarding the mechanisms involved in NP tolerance is limited. In this study, a batch of algal culture experiments were carried out to elucidate the underlying mechanisms by investigating the production and composition of extracellular polymeric substances (EPS) in algae exposed to NP. The excretion of EPS was significantly enhanced (P < 0.001) in algae exposed to 4 and 8 mg/L of NP. The polysaccharides in soluble EPS and the proteins in bound EPS were specifically overproduced. The three-dimensional excitation and emission matrix fluorescence spectra analyses indicated that tyrosine- and tryptophan-like substances were the main functional compositions in the proteins of EPS. In addition, enhanced EPS secretion significantly alleviated the toxicity of NP to the algae by the reduction of cell internalization, as indicated by the higher IC50, biomass, and cell growth rate in the algae with EPS. These discoveries along with the characterizations by algal cell surface hydrophobicity analysis, scanning electron microscopy, and Fourier transform infrared spectra spectroscopy demonstrated the vital role of EPS in the algal resistance to NP.

Bioaccumulation, growth performance, and transcriptomic response of Dictyosphaerium sp. after exposure to nonylphenol.

Algal cultures of Dictyosphaerium sp. were treated with a wide range (0-8 mg/L) of nonylphenol (NP) applications to investigate the species' potential to perform bioremediation of NP-contaminated wastewater and explore the mechanism of NP toxicity in algal cell. The algal species exhibited a high tolerance for NP and efficiently removed even high concentrations of NP. The accumulation of NP in algal cells tended to increase and the percentage of NP adhered to the cell walls tended to decrease as the NP concentration increased. The thylakoid density and the pyrenoid size also tended to decrease as the NP concentration rose. The key genes involved in the antioxidative pathways and photosynthetic pathways were down-regulated in the NP-treated algal cells. Algal ribosome genes were especially sensitive to NP. The results indicated that NP could induce oxidative stress in algal cells and that Dictyosphaerium sp. showed potential as a bioremediation agent.