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.

Eutrophication is an important water environment issue facing global lakes. Diversion of water from external watersheds into lakes is considered as effective in ameliorating eutrophication and reducing algal blooms. Nevertheless, the changes in lake water environment caused by external water diversion, especially the influence of water diversion on the characteristics of dissolved organic matters (DOM), are still poorly understood. We therefore used a combination of EEM-PARAFAC, Principal Component Analysis (PCA), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to investigate the effects of water diversion from the Niulan River on DOM characteristics in Lake Dianchi. The results showed that the water diversion from the Niulan River significantly improved the water quality of Lake Dianchi, the concentrations of TN, TP, COD and Chla decreased rapidly, and the degree of humification of dissolved organic matter (DOM) increased, which was in sharp contrast with that of pre-implementation. Firstly, the diversion of water from the Niulan River mainly led to changes in the structure of pollution sources. The load of influent rivers and sewage treatment plants rich in lignin and tannins increased, and the input of terrestrial humus increased. Second, the improved water quality reduced algal enrichment and frequency of blooms, and reduced the release of lipid- and protein-riched algal-derived DOM. Finally, the hydraulic retention time of Lake Dianchi caused by water diversion was shortened, the hydrodynamic conditions were significantly improved, and the dissolved oxygen (DO) level gradually recovered, which played a positive role in improving the humification degree of DOM. Our findings provide new insights for exploring the improvement of eutrophic lake eco-environmental quality caused by water diversion projects.

Aquatic plant biomass like Iris pseudacorus can be used as electron donor to improve denitrification performance in subsurface constructed wetlands. However, the phenomenon that the nitrogen removal rate declined in the terminal stage restricted the utilization of litters. In terms of this problem, this study investigated the performance of the used biomass through alkali treatment on nitrogen removal and analyzed the effect of alkali treatment on the component and structure of biomass and microbial community. The results showed that the alkali-treated biomass could further enhance the nitrogen removal by nearly 15% compared with used ones. The significant damage of cell walls and compact fibers containing cellulose and lignin through alkali treatment mainly resulted in the improvement of carbon release and nitrogen removal. With the addition of alkali-treated biomass, the richness index of microbes was higher compared with other biomass materials. Furthermore, the abundance of denitrification related genera increased and the abundance of genera for nitrification was maintained. Based on these finds, a mode of a more efficient Iris pseudacorus self-consumed subsurface flow constructed wetlands was designed. In this mode, the effluent total nitrogen could be stabilized below 5 mg L⁻¹ for nine months and the weight of litters could be further cut down by 75%. These findings would contribute to efficient utilization of plant biomass for nitrogen removal enhancement and final residue reduction in the wetlands.

The radial translocation of cadmium (Cd) from the root to the shoot is one of the major processes affecting Cd accumulation in rice (Oryza sativa L.) grains, but few studies have focused on Cd apoplastic transport in rice. The aim of this study was to determine how apoplastic barriers affect Cd translocation via the apoplastic pathway, Cd accumulation levels in upper parts (shoot and grains) of rice cultivars, and the possible mechanism involved. Hydroponic and soil pot trials were conducted to study the development and chemical constituents of apoplastic barriers and their permeability to bypass flow, and to determine Cd localization in the roots of rice cultivars with different Cd-accumulating characteristics. The Cd accumulation in upper parts was positively correlated with bypass flow in the root and the apparent Cd concentration in the xylem, indicating that the apoplastic pathway may play an important role in Cd root-shoot translocation in rice. Apoplastic barriers were deposited closer to the root tip and were thicker in low Cd-accumulating cultivars than in high Cd-accumulating cultivars. The amounts and rates of increase in lignin and suberin were significantly higher in ZD14 (a low Cd-accumulating cultivar) than in FYXZ (a high Cd-accumulating cultivar) under Cd stress, indicating that stronger barriers were induced by Cd in ZD14. The stronger and earlier formation of barriers in the low Cd-accumulating cultivar decreased bypass flow more efficiently, so that more Cd was retained in the root during apoplastic translocation. This was confirmed by localization analyses of Cd in root transverse sections. These results suggest that apoplastic barriers reduce Cd root-to-shoot translocation via the apoplastic pathway, leading to lower Cd accumulation in the upper parts of rice plants. Bypass flow may have the potential to be used as a rapid screening indicator for low Cd-accumulating rice cultivars.

Strategies for reducing cadmium (Cd) content in polluted farmland soils are currently limited. A type of composite with nanoparticles incorporated into a hydrogel have been developed to efficiently remove heavy metals from sewage, but their application in soils faces challenges, such as organic hydrogel degradation due to oxygen exposure and slow Cd²⁺ release from soil constituents. To overcome these challenges, a composite with superior stability for long-term application in soil is required. In this study, ferrous sulfide (FeS) nanoparticle@lignin hydrogel composites were developed. The lignin-based hydrogels inherited lignin’s natural mechanical and environmental stability and the FeS nanoparticles efficiently adsorbed Cd²⁺ and enhanced Cd²⁺ desorption from soils by producing H⁺. The high sorption capacity (833.3 g kg⁻¹) of the composite was attributed to four proposed mechanisms, including cadmium sulfide (CdS) precipitation via chemical reaction (84.06%), lignin complexation (13.19%), hydrogel swelling (0.61%), and nanoparticle sorption (2.15%). In addition, Fe²⁺ displaced from the composite was gradually oxidized to form solid iron oxide hydroxide, which increased Cd²⁺ sorption. The composite significantly reduced the total, surfactant-soluble, and fixed Cd in heavily and lightly polluted paddy soils by 22.4–49.6%, 13.5–68.6%, and 40.1–16.6%, respectively, in 7 days.

Proper management of waste crop residues has been an environmental concern for years. Yellow mealworms (larvae of Tenebrio molitor Linnaeus, 1758) are major insect protein source. In comparison with normal feed wheat bran (WB), we tested five common lignocellulose-rich crop residues as feedstock to rear mealworms, including wheat straw (WS), rice straw (RS), rice bran (RB), rice husk (RH), and corn straw (CS). We then used egested frass for the production of biochar in order to achieve clean production. Except for WS and RH, the crop residues supported mealworms’ life activity and growth with consumption of the residues by 90% or higher and degraded lignin, hemicellulose and cellulose over 32 day period. The sequence of degradability of the feedstocks is RS > RB > CS > WS > RH. Egested frass was converted to biochar which was tested for metal removal including Pb(II), Cd(II), Cu(II), Zn(II), and Cr(VI). Biochar via pyrolysis at 600 °C from RS fed frass (FRSBC) showed the best adsorption performance. The adsorption isotherm fits the Langmuir model, and kinetic analysis fits the Pseudo-Second Order Reaction. The heavy metal adsorption process was well-described using the Intra-Particle Diffusion model. Complexation, cation exchange, precipitation, reduction, deposition, and chelation dominated the adsorption of the metals onto FRSBC. The results indicated that crop residues (WS, RS, RB, and CS) can be utilized as supplementary feedstock along with biochar generated from egested frass to rear mealworms and achieve clean production while generating high-quality bioadsorbent for environment remediation and soil conditioning.

Creosol and 4-ethylguaiacol are two important methoxyphenols, lignin pyrolysis products, which are discharge into the atmosphere in large quantities. In this work, theoretical calculations of the reaction mechanism towards the two compounds with NO₃ radicals was performed using DFT method. The rate constants and toxicity assessment were also investigated. The atmospheric lifetime for creosol and 4-ethylguaiacol were 0.82 and 0.19 h, respectively. A new reaction pathway was proposed for the transformation of methoxyl into hydroxyl, which has not yet been clarified in previous studies. The toxicity of methoxyphenols and their degradation products is closely related to their hydrophobicity. Although most degradation products are less toxic, they also should be pay more attention, especially for nitro-substituents.A new reaction pathway was proposed for the transformation of methoxyl into hydroxyl. The toxicity is closely related to their hydrophobicity.

Sediments from a waste pit in Houston Ship Channel (HSC) were characterized using a number of molecular markers of natural organic matter fractions (e.g., pyrogenic carbon residues, PAHs, lignins), in addition to dioxins, in order to test the hypothesis that the dispersal and mobility of dioxins from the waste pit in the San Jacinto River is minimal. Station SG-6, sampled at the site of the submerged waste pit, had the highest dioxin/furan concentrations reported for the Houston Ship Channel/Galveston Bay (HSC/GB) system (10,000–46,000 pg/g), which translated into some of the highest reported World Health Organization Toxic Equivalents (TEQs: 2000–11,000 pg/g) in HSC sediments. Using a multi-tracer approach, this study confirmed our hypothesis that sludges from chlorinated pulps are a very likely source of dioxins/furans to this pit. However, this material also contained large quantities of additional hydrophobic organic contaminants (PAHs) and pyrogenic markers (soot-BC, levoglucosan), pointing to the co-occurrence of petroleum hydrocarbons and combustion byproducts. Comparison of dioxin/furan signatures in the waste pit with those from sediments of the HSC and a control site suggests that the remobilization of contaminated particles did not occur beyond the close vicinity of the pit itself. The dioxins/furans in sediments outside the waste pit within the HSC are rather from other diffuse inputs, entering the sedimentary environment through the air and water, and which are comprised of a mixture of industrial and municipal sources. Fingerprinting of waste pit dioxins indicates that their composition is typical of pulp and paper sources. Measured pore water concentrations were 1 order of magnitude lower than estimated values, calculated from a multiphase sorption model, indicating low mobility of dioxins within the waste pit. This is likely accomplished by co-occurring and strong sorbing pyrogenic and petrogenic residues in the waste pit, which tend to keep dioxins strongly sorbed to particles.

Knowledge of adsorption behavior of organic contaminants on high heat temperature treated biochars is essential for application of biochars as adsorbents in wastewater treatment and soil remediation. In this study, isotherms of 25 aromatic compounds adsorption on biochars pyrolyzed at 700 °C from biomass including wood chips, rice straw, bamboo chips, cellulose, lignin and chitin were investigated to establish correlations between adsorption behavior and physicochemical properties of biochars. Isotherms were well fitted by Polanyi theory-based Dubinin-Ashtakhov (DA) model with three parameters, i.e., adsorption capacity (Q⁰) and adsorption affinity (E and b). Besides the negative correlation of Q⁰ with molecular maximum cross-sectional areas (σ) of organic compounds, positive correlations of Q⁰ with total pore volume (Vₜₒₜₐₗ) and average diameter of micropore (D) of biochars were observed, indicating that adsorption by biochars is captured by the pore-filling mechanism with molecular sieving effect in biochar pores. Linear solvation energy relationships (LSERs) of adsorption affinity (E) with solvatochromic parameters of organic compounds (i. e., αₘ and π∗) were established, suggesting that hydrophobic effect, π-π interaction and hydrogen-bonding interaction are the main forces responsible for adsorption. The regression coefficient (π₁) and intercept (C) of obtained LSERs are correlated with biochar H/C and Rₘᵢcᵣₒ, respectively, implying that biochars with higher aromaticity and more micropores have stronger π-π bonding potential and hydrophobic effect potential with aromatic molecule, respectively. However, hydrogen-bonding potential of biochars for organic molecules is not changed significantly with properties of biochars. A negative correlation of b with biochar H/C is also obtained. These correlations could be used to predict the adsorption behavior of organic compounds on high heat temperature treated biochars from various biomass for the application of biochars as sorbents and for the estimating of environmental risks of organic compounds in the present of biochars.

The desorption kinetics and mechanism were investigated using a Tenax extraction technique on different sediments spiked with radiocarbon-labeled benzo[a]pyrene (BaP). Five sedimentary fractions were sequentially fractionated, and the only nonhydrolyzable organic carbon fractions (NHC) were characterized using advanced solid-state 13C nuclear magnetic resonance spectroscopy (NMR), improved six end-member model, and a CO2 gas adsorption technique. The sediments contained high percentages of algaenan and/or sporopollenin but low percentages of black carbon and lignin. A first-order, two-compartment kinetics model described the desorption process very well (R2 > 0.990). Although some of the organic carbon fractions were significantly related to the desorption kinetics parameters, the NHC fractions showed the highly significant correlation. Moreover, the nanoporosity or specific surface area (SSA) of the NHC fractions was highly related to their OC contents and aliphatic C (R2 = 0.960, p < 0.01). The multiple regression equations among the desorption kinetics parameters, structural parameters, and nanoporosity were well established (R2=>0.999). Nanoporosity and aromatic C were the dominant contributors. Furthermore, the enhanced percentages of desorbed BaP at elevated temperatures significantly showed a linear regression with the structure and nanoporosity. To our knowledge, the above evidence demonstrates for the first time that the transfer (or diffusion) of BaP in the nanopores of condensed aromatic components is the dominant mechanism of the desorption kinetics of BaP at organic matter particle scale.