Quinone is the important redox functional group for electron transfer capacity (ETC) of humic acid (HA). Lignin, as major component in corn straw, can be decomposed into phenol monomers, then oxidation into quinones for synthesis of HA during composting process. However, it is still unclear that the effects of type and variation characteristics of phenol monomers on redox characteristics of HA during straw composting process. In this study, p-hydroxybenzoic acid (P1), vanillic acid (P2), syringic acid (P3), p-hydroxy benzaldehyde (P4), 4-coumaric acid (P5), 4-hydroxyacetophenone (P6), ferulic acid (P7) and 4-hydroxy-3-methylacetophenone (P8) were recognized and clustered into three groups. The concentration of polyphenol presented a significant downward trend during the straw composting process. Based on the relationships among phenol monomers to ETC, electron donating capacity (EDC), electron accepting capacity (EAC) and quinone, we found that P1, P2, P3, P5 and P7 were significantly related to ETC, EDC and EAC of HA (P < 0.05). Furthermore, NH₄⁺-N and NO₃⁻-N were the main micro-environmental factors linking to ETC-related phenol monomers and redox characteristics of HA in straw composts (P < 0.05). Finally, two groups of core microflora that promoting the ETC-related phenol monomers and NH₄⁺-N, and ETC-related phenol monomers and NO₃⁻-N were identified by Mantel test, respectively. This study contributes a new insight for polyphenol way for redox capacity of HA in traditional composting and utilization of straw compost in contaminated environments.

Wastewater treatment plants (WWTPs) are almost the only place where plastic fragments are artificially removed, resulting in mass accumulation of nanoplastics (NPs). In this research, four different concentrations (0 mg/L, 0.1 mg/L, 1 mg/L, 10 mg/L) of polystyrene nanoplastics (PS-NPs) were used to investigate the cell damage and nitrogen inhibition of activated sludge, exposed in a self-assembled SBR reactor for 30 days. Intracellular reactive oxides (ROS) and extracellular lactate dehydrogenase (LDH) increased with the rise of exposure concentration, and morphological analysis disclosed the creases, collapse, and even rupture of cell membranes. However, exposure damage (PS-NPs ≤ 1 mg/L) appeared to be reversible, attributed to that extracellular polymeric substances (EPS) secretion can thicken the three protective layers outside the membrane. PS-NPs did not disrupt the EPS chemical structure, but increased humic acid content. Prolonged exposure time (from 15 to 30 days) was directly related to the nitrogen inhibition. Due to the habitat changes under PS-NPs exposure, abundance and diversity of microorganisms in the original activated sludge decreased significantly, and the dominant phylum was occupied by Patescibacteria (PS-NPs = 10 mg/L). Changes in enzyme activities of AMO, NR, NIR, and NOR with exposure concentration may explain the conversion of nitrogen in SBR. This research broadens our horizons to understand the response mechanism of activated sludge bacteria to PS-NPs exposure individually and collectively.

In this study, magnetic biochar (MAB) and humic acid (HA)-coated magnetic biochar produced from apple branches without and after cellulase hydrolysis (HMAB and CHMAB, respectively) were prepared and tested as adsorbents of enrofloxacin (ENR) and moxifloxacin (MFX) in aqueous solution. Compared with MAB and HMAB, novel adsorbent CHMAB possessed a superior mesoporous structure, greater graphitization degree and abundant functional groups. When antibiotic solutions ranged from 2 to 20 mg L⁻¹, the theoretical maximum adsorption capacities of CHMAB for ENR and MFX were 48.3 and 61.5 mg g⁻¹ at 35 °C with adsorbent dosage of 0.4 g L⁻¹, respectively, while those of MAB and HMAB were 39.6 and 54.4 mg g⁻¹, and 44.7 and 59.0 mg g⁻¹, respectively. The pseudo-second-order kinetic model and Langmuir model presented a better fitting to the spontaneous and endothermic adsorption process. The maximum adsorption capacity of ENR and MFX onto CHMAB was achieved at initial pH values of 5 and 8, respectively. Additionally, the adsorption capacity of ENR and MFX decreased with increasing concentrations of K⁺ and Ca²⁺ (0.02–0.1 mol L⁻¹). Synergism between the pore-filling effect, π-π electron-donor-acceptor interactions, regular and negative charge-assisted H-bonding, surface complexation, electrostatic interactions and hydrophobic interactions may dominate the adsorption process. This study demonstrated that a novel magnetic biochar composite prepared through pyrolysis of agricultural waste lignocellulose hydrolyzed by cellulase in combination with HA coating was a promising adsorbent for eliminating quinolone antibiotics from aqueous media.

The decay of algal biomass and aquatic plants in freshwater lakes leads to the overproduction of autochthonous organic matter (OM) and the exhaustion of dissolved oxygen, impacting the microbial community and subsequent biodegradation of emerging contaminants in sediment. This study explored how the microbial processing of aquatic plant- and algal-derived OM (POM and AOM) mediates 17α-ethinylestradiol (EE2) biodegradation in the anoxic sediments of Lake Taihu in China. In four months of microcosm incubations, the increased concentrations of protein-like substances in AOM and POM exhibited temporary activation on microbial metabolic enzyme activity (fluorescein diacetate hydrolase and dehydrogenase) and significantly promoted the carbon mineralization with iron reduction (P < 0.001). These in turn increased the EE2 biodegradation efficiency to 77–90 ng g⁻¹ in the anoxic sediment. However, a higher EE2 biodegradation of 109 ng g⁻¹ was achieved with the humic acid augmentation containing more quinone-like compounds, showing a weaker substrate-priming effect but accelerated redox cycling of iron and organic substrates in the later period of incubation. The microbial analysis further revealed that the quinone-like compounds in OM were more closely associated with microbial electron transfer and strengthened their interspecies syntrophic cooperation favorable to contaminant biodegradation, even though the connective members exposed to protein-like components upregulated more functional genes related to organic carbon and xenobiotics metabolism and biodegradation. Our findings will help predict the fate of estrogens in various sedimentary environments under increasing eutrophication and further climate change scenarios.

Per- and polyfluoroalkyl substances (PFASs) have been found to be widely present in soil. Dissolved organic matter (DOM) in soil are supposed to greatly affect the bioavailability of PFASs in soil. Herein, hydroponic experiments were conducted to understand the impacts of two kinds of typical DOM, bovine serum albumin (BSA) and humic acid (HA), on the uptake and translocation of legacy PFASs and their emerging alternatives, perfluorooctane sulfonic acid (PFOS), perfluorooctane acid (PFOA), perfluorohexane sulfonic (PFHxS) and 6:2 chlorinated polyfluoroalkyl ether sulfonate (6:2 Cl-PFESA) in wheat (Triticum aestivum L.). The results indicated that both HA and BSA significantly inhibited the bioaccumulation and translocation of PFASs in the roots and shoots of wheat, and the impacts of BSA were greater than HA. This difference was explained by the greater binding affinities of the four PFASs with BSA than with HA, as evidenced by the equilibrium dialysis and isothermal titration calorimetry (ITC) analyses. It was noting that inhibition impacts of the BSA-HA mixture (1:1) were lower than BSA alone. The results of Fourier transform infrared (FT-IR) spectroscopy and excitation-emission matrix (EEM) fluorescence spectroscopy suggested that HA could bind with the fluorescent tryptophan residues in BSA greatly, competing the binding sites with PFASs and forming a cover on the surface of BSA. As a result, the binding of PFASs with BSA-HA complex was much lower than that with BSA, but close to HA. The results of this study shed light on the impacts of DOM in soil on the bioaccumulation and translocation of PFASs in plants.

This study demonstrated that nitrogen-doped carbon materials (NCMs) could effectively catalyze the chlorine elimination process in hexachloroethane (HCA) declorination in sulfide-containing environments for the first time. The kₒbₛ values of HCA dechlorination by sulfide in the presence of 10 mg/L NCMs were higher than that of no mediator at pH 7.3 by one or two orders of magnitude. The catalytic capabilities of NCMs on HCA dechlorination were evident in common ranges of natural pH (5.3–8.9) and it could be accelerated by the increase of pH but be suppressed by the presence of dissolved humic acid. Moreover, NCMs exhibited much better catalytic capability on HCA dechlorination compared to the carbon materials, mainly owing to the combined contributions of pyridine N, including enhanced nucleophilic attack to HCA molecule by generating newborn C–S–S and activation of HCA molecule by elongating C–Cl bonds. The functions of pyridine N in micron-sized NCMs with mesopores were better than in nano-sized NCMs on HCA dechlorination. These findings displayed the potential of NCMs, when released into sulfide-containing environments, may significantly increase the dechlorination of chlorinated aliphatic hydrocarbons.

Effluent is often treated with ozone before being discharged into a natural water environment. This process will change the interaction between effluent organic matter and pollutants in aquatic environment. The impact of ozonation on complexation between dissolved organic matter in such wastewater and sulfadimidine often found in natural water was studied in laboratory experiments using four types of real wastewater. Ozonation was found to decrease the proportion of organic matter with a molecular weight greater than 5 kDa as well as protein-like, fulvic-like and humic-like components, but except the proportion of hydrophilic components. The aromaticity of the dissolved organic matter was also reduced after ozonation. The complexation of tryptophan and tyrosine with sulfadimidine mainly depends on their hydrophobicity and large molecular weight. Ozonation of fulvic and humic acid tends to produce small and medium molecular weight hydrophilics. The complexation of humic and fulvic acids with sulfadimidine was enhanced by ozonation. Dissolved organic matter, with or without oxidation, were found to weaken sulfadimidine’s inhibition of microbial growth, especially for Aeromonas and Acinetobacter species. This finding will expand our understanding about the impact of advanced treatment processes on the dissolved organic matters’ properties in effluent.

Copper ferrite (denoted as CuFe₂O₄MOF), prepared via a complexation reaction to obtain bimetal–organic frameworks (Cu/Fe bi-MOFs), followed by a combustion process to remove the MOF template, is employed as a heterogeneous activator to promote sulfite autoxidation for the removal of organic contaminants. At pH 8.0, more than 80% of the recalcitrant organic contaminant iohexol (10 μM) can be removed within 2 min by the activation of sulfite (500 μM) with CuFe₂O₄MOF (0.1 g L⁻¹). CuFe₂O₄MOF exhibits more pronounced catalytic activity in accelerating sulfite autoxidation for iohexol abatement compared to that fabricated by hydrothermal and sol–gel combustion methods. Radical quenching studies suggest that the sulfate radical (SO₄•⁻) is the main reactive species responsible for iohexol abatement. The performance of CuFe₂O₄MOF/sulfite for iohexol abatement can be affected by several critical influencing factors, including the solution pH and the presence of humic acid, Cl⁻, and HCO₃⁻. The effect of the ionic strength and the results of the attenuated total reflectance–Fourier transform infrared (ATR–FTIR) analysis indicate that sulfite autoxidation in the presence of CuFe₂O₄MOF involves an inner-sphere interaction with the surface Cu(II) sites of CuFe₂O₄MOF. X-ray photoelectron spectroscopy (XPS) characterization suggests that the surface Cu(II)–Cu(I)–Cu(II) redox cycle is responsible for efficient SO₄•⁻ production from sulfite. Overall, CuFe₂O₄MOF can be considered an alternative activator for sulfite autoxidation for potential application in the treatment of organic-contaminated water.

Previous studies have indicated that natural organic matter in the aquatic environment could affect arsenic bioaccumulation and biotransformation to aquatic organisms. However, the differences between the effects of arsenite and arsenate exposure have not been studied and compared in fish exposure models. In this study, adult zebrafish (Danio rerio) were exposed to 5 mg/L inorganic As solutions, in the presence of a range of humic acid (HA) concentrations (1, 2.5, 5, 10, 20 mg/L) in 96 h waterborne exposure. Results showed that in the presence of HA, total As bioaccumulation was significantly reduced in zebrafish following arsenite exposure, while this reduction was not observed during arsenate exposure. The reduction in total arsenic bioaccumulation for arsenite exposure can be explained by the fact that HA forming a surface coating on the cell surface, hindering transport and internalization. However, this reduction in total As was not observed due to differences in uptake pathways for arsenate exposure. Results also showed that Arsenobetaine (AsB) was the main biotransformation product in zebrafish following inorganic As exposure, accounting for 44.8%–64.7% of extracted arsenic species in all exposure groups. The addition of HA caused levels of MMA and As(III) to decrease, while the distribution of AsB significantly increased in arsenite exposure groups. The increase in AsB could be because the As(III)-HA complex was formed, affecting the methylation of As(III). In contrast, the addition of HA to arsenate exposure groups, did not affect the reduction of As(V) to As(III) and therefore, an increase in the distribution of AsB was not observed in arsenate exposure groups. This study provides useful information on the mechanisms of toxicity, for improved risk assessment of As in natural aquatic environments.

The present work was done to explore the joint effect of Streptomyces pactum (Act12) and plant nutrients on phytoremediation of smelter-contaminated soils. The physiological indicators and phytoextraction indices of potherb mustard (Brassica juncea, Coss) grown in Act12 inoculated soil with or without Hoagland’s solution (H), humic acid (HA) and peat (PS) were evaluated. The results indicated that H, HA and PS acted synergistically with Act12, notably increasing chlorophyll and soluble protein contents and thereby promoting plant growth. Soil nutrient treatments reduced the antioxidant activities (PPO, CAT and POD) by 28.2–41.4%, 22.3–90.1% and 15.2–59.4% compared to control, respectively. Act12 and H treatments markedly facilitated plant to accumulate more cadmium (Cd) and zinc (Zn), but it was observed decreases when applied with HA and PS. Metal uptake (MU) values further indicated the differences in phytoextraction efficiency, i.e., H > PS > Control > HA. Taken together, Act12 combined with plant nutrients contributed to alleviating metal toxicity symptoms of plant. Hoagland’s solution and peat were highlighted in the present phytoextraction trial, and recommended as soil additives.