Hydrochar and Its Dissolved Organic Matter Aged in a 30-Month Rice-Wheat Rotation System: Do Primary Aging Factors Alter at Different Stages?

Hydrochar, recognized as a green and sustainable soil amendment, has garnered significant attention. However, information on the aging process in soil and the temporal variability of hydrochar remains limited. This study delves deeper into the interaction between hydrochar and soil, focusing on primary factors influencing hydrochar aging during a 30-month rice-wheat rotation system. The results showed that the initial aging of hydrochar (0-16 months) is accompanied by the development of specific surface area and leaching of hydrochar-derived dissolved organic matter (HDOM), resulting in a smaller particle size and reduced carbon content. The initial aging also features a mineral shield, while the later aging (16 to 30 months) involves surface oxidation. These processes collectively alter the surface charge, hydrophilicity, and composition of aged hydrochar. Furthermore, this study reveals a dynamic interaction between the HDOM and DOM derived from soil, plants, and microbes at different aging stages. Initially, there is a preference for decomposing labile carbon, whereas later stages involve the formation of components with higher aromaticity and molecular weight. These insights are crucial for understanding the soil aging effects on hydrochar and HDOM as well as evaluating the interfacial behavior of hydrochar as a sustainable soil amendment.

Knowledge graph and development hotspots of biochar as an emerging aquatic antibiotic remediator: A scientometric exploration based on VOSviewer and CiteSpace.

As an emerging material in the field of environmental remediation, biochar produced by carbonisation of organic solid waste has been widely used in the remediation of antibiotic wastewater due to its environmental friendliness and excellent adsorption properties. This study analyses the current literature in the field in a comprehensive and scientific manner using CiteSpace and VOSviewer technologies. Between 2011 and 2023, a total of 1162 papers were published in this domain, spanning three distinct stages: applied methods, mechanism investigation, and enhanced improvement. The results of keyword clustering indicate that the remediation of antibiotics complexed with multiple pollutants by biochar is the main research topic, followed by the remediation of antibiotics by biochar in combination with other technologies. Furthermore, drawing from current research hotspots in antibiotic remediation using biochar, this study identified the pivotal mechanisms involved: (1) The primary mechanisms by which raw biochar remediates antibiotics include π-π electron donor-acceptor interactions, hydrophobic interactions, electrostatic interactions, hydrogen-bonding, and pore filling. (2) Steam activation, acid/base, metal salt/metal oxide, and clay mineral modification can improve the physical/chemical properties of biochar, enhancing its adsorptive removal of antibiotics. (3) Biochar activated persulfate and degraded antibiotics via free radical pathways (SO4-•, •OH and O2-•) as well as non-free radical pathways (1O2 and electron transfer). In addition, the challenge and prospect of biochar engineering applications for antibiotic remediation lies in improving the main mechanism of antibiotic remediation by biochar. The prospective utilization of biochar in enhancing the remediation of antibiotic-related pollutants holds tremendous value for the future.

Unraveling the photochemical behavior of dissolved organic matter derived from hydrothermal carbonization process water: Insights from molecular transformation and photoactive species.

Hydrothermal carbonization process water (HTPW) has been utilized as a substitute for chemical fertilizers in agricultural applications. However, the input of HTPW into paddy water, particularly the significant proportion of dissolved organic matter (DOM) in HTPW (DOM-HTPW), directly engages in photochemical transformations, a phenomenon often overlooked. This study observed a consistent decrease in humification (SUVA280, 7.7-53.9%) and aromaticity (SUVA254, 6.1-40.0%) of DOM-HTPW after irradiation. The primary active photobleaching components of DOM-HTPW varied depending on the feedstock, such as protein for chicken manure DOM-HTPW and lignin for rice straw DOM-HTPW. The photochemical activity of DOM-HTPW was augmented by its lower molecular weight and higher hydrophilic composition, particularly evident in chicken manure DOM-HTPW, which exhibited higher generation rates for 1O2 (35.1-37.1%), 3DOM* (32.8-43.9%), and O2•- (28.6-48.8%) as measured by molecular probes. DOM-HTPW effectively facilitated the phototransformation of tetracycline, with the contribution of O2•- being more significant than 3DOM* and 1O2. These findings shed new light on the understanding the photochemical processes of DOM-HTPW as exogenous DOM and the interconnected fate of contaminants in aquatic environments.

Biochar and hydrochar application influence soil ammonia volatilization and the dissolved organic matter in salt-affected soils.

Biochar, which including pyrochar (PBC) and hydrochar (HBC), has been tested as a soil enhancer to improve saline soils. However, the effects of PBC and HBC application on ammonia (NH3) volatilization and dissolved organic matter (DOM) in saline paddy soils are poorly understood. In this research, marsh moss-derived PBC and HBC biochar types were applied to paddy saline soils at 0.5 % (w/w) and 1.5 % (w/w) rates to assess their impact on soil NH3 volatilization and DOM using a soil column experiment. The results revealed that soil NH3 volatilization significantly increased by 56.1 % in the treatment with 1.5 % (w/w) HBC compared to the control without PBC or HBC. Conversely, PBC and the lower application rate of HBC led to decrease in NH3 volatilization ranging from 2.4 % to 12.1 %. Floodwater EC is a dominant factor in NH3 emission. Furthermore, the fluorescence intensities of the four fractions (all humic substances) were found to be significantly higher in the 1.5 % (w/w) HBC treatment applied compared to the other treatments, as indicated by parallel factor analysis modeling. This study highlights the potential for soil NH3 losses and DOM leaching in saline paddy soils due to the high application rate of HBC. These findings offer valuable insights into the effects of PBC and HBC on rice paddy saline soil ecosystems.

One-step synthesis of phytic acid-assisted hydrochar boost selective sorption and in situ passivation of lanthanum.

The rare earth metal element lanthanum (La) possesses carcinogenic, genotoxic, and accumulative properties, necessitating urgent development of an efficient and cost-effective method to remove La. However, current sorbents still encounter challenges such as poor selectivity, low sorption capacity, and high production costs. This study therefore proposes a promising solution: the creation of phytic acid-assisted sludge hydrochars (P-SHCs) to eliminate La from water and soil environments. This method harnesses phytic acid's exceptional binding ability and the economical hydrothermal carbonization process. P-SHCs exhibit robust sorption affinity, fast sorption kinetics, and excellent sorption selectivity for La when compared with pristine hydrochars (SHCs). This advantage arises from the remarkable binding ability of phosphate functional groups (polyphosphates) on P-SHCs, forming P-O-La complexes. Moreover, P-SHCs demonstrate sustained sorption efficiency across at least five cycles, with a slight decrease attributed to the loss of phosphorus species and mass during recycling. Furthermore, P-SHCs demonstrated superior economic feasibility, with a higher estimated cost-benefit ratio than that of other sorbents. Our study further validates the exceptional passivation capability of P-SHCs, showcasing relative stabilization efficiency ranging from 37.6 % to 79.6 % for La contamination. Additionally, acting as soil passivation agents, P-SHCs foster the enrichment of specific soil microorganisms such as Actinobacteria and Proteobacteria, capable of solubilizing phosphorus and resisting heavy metals. These findings present novel ideas and technical support for employing P-SHCs in combatting environmental pollution stemming from rare earth metals.

Biodegradable microplastics aging processes accelerated by returning straw in paddy soil.

Biodegradable microplastics (MPs) have been released into agricultural soils and inevitably undergo various aging processes. Straw return is a popular agricultural management strategy in many countries. However, the effect of straw return on the aging process of biodegradable MPs in flooded paddy soil, which is crucial for studying the characteristics, fate, and environmental implications of biodegradable MPs, remains unclear. Here, we constructed a 180-day microcosm incubation to elucidate the aging mechanism of polylactic acid (PLA)-MPs in straw-enriched paddy soil. This study elucidated that the prominent aging characteristic of PLA-MPs occurred in the straw-enriched paddy soil, accompanied by increased chrominance (76.64-182.3 %), hydrophilicity (2.92-22.07 %), roughness (33.12-58.01 %), and biofilm formation (42.12-100.3 %) for the PLA-MPs, especially with 2 % (w/w) straw return treatment (P < 0.05). A 2 % straw return treatment has significantly impacted ester CO group changes in PLA-MPs, altered the MPs-attached soil bacterial communities composition, strengthened bacterial network structure, and increased soil proteinase K activity. The findings of this work demonstrated that flooded, straw-enriched paddy soil accelerated PLA-MPs aging affected by soil-water chemistry, soil microbe, and soil enzymatic. This study helps to deepen our understanding of the aging process of PLA-MPs in straw return paddy soil. ENVIRONMENTAL IMPLICATION: Microplastics (MPs) are emerging contaminants in the global soil and terrestrial ecosystems. Biodegradable MPs are more likely to be formed and released into agricultural soils during aging. Straw return is a popular agricultural management strategy in many countries. Considering the wide use of plastic film, sewage sludge, plastic-coated fertilizer, and organic fertilizer in agricultural ecosystems, it is crucial to pay attention to the aging process of biodegradable MPs in straw-enriched paddy soil, which has not been adequately emphasized. This aspect has been overlooked in previous studies and threatens ecosystems. This study demonstrated that straw-enriched paddy soil accelerated polylactic acid (PLA)-MPs aging influenced by the dissolved organic matter, microorganisms, and enzyme activity associated with straw decomposition.

Microplastics alter soil structure and microbial community composition.

Microplastics (MPs), including conventional hard-to-biodegrade petroleum-based and faster biodegradable plant-based ones, impact soil structure and microbiota in turn affecting the biodiversity and functions of terrestrial ecosystems. Herein, we investigated the effects of conventional and biodegradable MPs on aggregate distribution and microbial community composition in microhabitats at the aggregate scale. Two MP types (polyethylene (PE) and polylactic acid (PLA) with increasing size (50, 150, and 300 µm)) were mixed with a silty loam soil (0-20 cm) at a ratio of 0.5 % (w/w) in a rice-wheat rotation system in a greenhouse under 25 °C for one year. The effects on aggregation, bacterial communities and their co-occurrence networks were investigated as a function of MP aggregate size. Conventional and biodegradable MPs generally had similar effects on soil aggregation and bacterial communities. They increased the proportion of microaggregates from 17 % to 32 %, while reducing the macroaggregates from 84 % to 68 %. The aggregate stability decreased from 1.4 mm to 1.0-1.1 mm independently of MP size due to the decline in the binding agents gluing soil particles (e.g., microbial byproducts and proteinaceous substances). MP type and amount strongly affected the bacterial community structure, accounting for 54 % of the variance. Due to less bioavailable organics, bacterial community composition within microaggregates was more sensitive to MPs addition compared to macroaggregates. Co-occurrence network analysis revealed that MPs exacerbated competition among bacteria and increased the complexity of bacterial networks. Such effects were stronger for PE than PLA MPs due to the higher persistence of PE in soils. Proteobacteria, Bacteroidetes, Chloroflexi, Actinobacteria, and Gemmatimonadetes were the keystone taxa in macroaggregates, while Actinobacteria and Chloroflexi were the keystone taxa in microaggregates. Proteobacteria, Actinobacteria, and Chloroflexi were the most sensitive bacteria to MPs addition. Overall, both conventional and biodegradable MPs reduced the portion of large and stable aggregates, altering bacterial community structures and keystone taxa, and consequently, the functions.

Sustainable design of photo-Fenton-like oxidation process in actual livestock wastewater through the highly dispersed FeCl3 anchoring on a g-C3N4 substrate.

Photocatalytic technology emerges as a promising solution for the sustainable treatment of contaminated wastewater. However, the practical implementation of designed photocatalysts often faces challenges due to the intricate 'high carbon footprint' process and limited outdoor laboratory investigations. Herein, a simple yet versatile impregnation approach is proposed to anchor highly dispersed FeCl3 on a g-C3N4 substrate (Fe-C3N4) with minimal energy consumption and post-processing. Fe-C3N4 enhances photocatalytic reactivity for antibiotic degradation via a synergistic photo-Fenton-like oxidation technique, efficiently removing antibiotic pollutants from actual livestock wastewater. The Fe-C3N4 catalyst exhibited consistent degradation performance over five cycles in laboratory conditions, maintaining a degradation efficiency exceeding 90 % for tetracycline hydrochloride (TCHCl). Furthermore, we engineered a straightforward Fe-C3N4Na2SiO3 reactor for treating livestock wastewater, achieving an 81.8 % removal of TCHCl in outdoor field tests conducted in the winter and summer in China. The Fe-C3N4 catalyst demonstrated high feasibility in treating antibiotic-contaminated livestock wastewater under year-round climatic conditions, leveraging synergistic effects. The stabilization of Fe-C3N4 for the degradation of antibiotic-containing wastewater under sunlight represents a significant advancement in the practical application of photocatalysts, marking a crucial milestone from experimental conception to implementation. Acute toxicity estimation suggested that intermediates/products generated exhibited lower toxicity compared to TCHCl, indicating their practical applicability. Density functional theory (DFT) analysis successfully predicted significant electron transfer between Fe-C3N4 and TCHCl, indicating efficient interfacial interactions on the TCHCl surface. To ensure the environmental sustainability of Fe-C3N4, a life cycle assessment (LCA) was conducted to compared this photocatalyst with other commonly used emerging photocatalysts. The results demonstrated that Fe-C3N4 exhibits a two orders of magnitude lower CO2 equivalent emission compared to the ZnO photocatalyst, indicating a cost-effective and efficient synergistic photo-Fenton-like catalytic approach. This low-cost photocatalyst, moving from the laboratory to real-world wastewater applications, provides a powerful and more sustainable solution for the efficient treatment of wastewater containing antibiotics from livestock farming.

Manure derived hydrochar reduced phosphorus loss risk via an alteration of phosphorus fractions and diversified microbial community in rice paddy soil.

Phosphorus (P) loss caused by the irrational use of manure organic fertilizer has become a worldwide environmental problem, which has caused a potential threat to water safety and intensified agricultural non-point source pollution. Hydrothermal carbonization is method with a low-energy consumption and high efficiency to deal with environmental problems. Application of pig manure-derived hydrochar (PMH) to soil exhibited potential of sustainable development compared with the pristine pig manure (PM). However, the effects of PMH on the distribution of P among the fractions/forms and the interaction between microorganisms and P forms and its relevance to the potential loss of P in paddy fields has not been clarified. Therefore, in this study, a soil column experiment was conducted using the untreated soil (control), and the PM, PMH1 (PMH derived at 180 °C), and PMH2 (PMH derived at 260 °C) treated soils (at the dose of 0.05 %) and rice was cultivated to investigate the effects of PM and PMH on the P fractions, mobilization, ad potential loss via the induced changes on soil microbial community after a complete growing season of rice. The trend of P utilization was evaluated by P speciation via continuous extraction and 31P NMR. The addition of PMH reduced the proportion of residual P in soil by 23.8-26.3 %, and increased the proportion of HCl-P and orthophosphate by 116.2-158.6 % and 6.1-6.8 % compared to PM. The abundance of gcd gene developed after the application of PMH2, which enhanced the mobile forms of soil P utilization via secreting gluconic acid. The network diagram analysis concluded that the changes in various P forms were mainly related to Proteobacteria, Bacteroides, Firmicutes and Acidobacteria. The results illustrated that PMH mitigate the potential risk of P loss more than PM by altering P fractions and affecting soil microbial community.

Programmable "triple attack" cancer therapy through in situ activation of disulfiram toxification combined with phototherapeutics.

Effectively and completely eliminating residual tumor cells is the key to reducing the risk of tumor metastasis and recurrence. Designing an "ideal" nanoplatform for programmable cancer therapy has great prospects for completely eliminating residual tumor cells. Herein, an intelligent nanoplatform of disulfiram (DSF)-loaded CuS-tannic acid nanohexahedrons (denoted as "DSF-CuS@TA") with thermal- and pH-sensitive degradation, as well as near-infrared (NIR-II) phototherapeutics properties, was constructed. And then, it was employed for in situ DSF toxification activation programmable "triple attack" cancer therapy. After accumulating in the tumor, DSF-CuS@TA first releases the loaded Cu(DTC)2, and simultaneously degrades and releases Cu2+ and DSF under mildly acidic stimulation to trigger instant intratumoral Cu(DTC)2 chelation, thereby achieving the "first strike." Next, under irradiation by a NIR-II laser, light energy is converted into heat to generate NIR-II photothermal therapy, thereby achieving the second strike. Subsequently, under thermal stimulation, DSF-CuS@TA degrades further, triggering the chelation of Cu(DTC)2 for a second time to reach the third strike. As expected, in vitro and in vivo studies showed that the synergistic integration of DSF-based programmed chemotherapy and NIR-II phototherapeutics could achieve effective tumor removal. Therefore, we propose a novel type of programmed therapy against cancer by designing a nanoplatform via "nontoxicity-to-toxicity" chemical chelation transformation.

Efficient magnetic capture of PE microplastic from water by PEG modified Fe3O4 nanoparticles: Performance, kinetics, isotherms and influence factors.

Due to their resistance to degradation, wide distribution, easy diffusion and potential uptake by organisms, microplastics (MPs) pollution has become a major environmental concern. In this study, PEG-modified Fe3O4 magnetic nanoparticles demonstrated superior adsorption efficiency against polyethylene (PE) microspheres compared to other adsorbents (bare Fe3O4, PEI/Fe3O4 and CA/Fe3O4). The maximum adsorption capacity of PE was found to be 2203 mg/g by adsorption isotherm analysis. PEG/Fe3O4 maintained a high adsorption capacity even at low temperature (5°C, 2163 mg/g), while neutral pH was favorable for MP adsorption. The presence of anions (Cl-, SO42-, HCO3-, NO3-) and of humic acids inhibited the adsorption of MPs. It is proposed that the adsorption process was mainly driven by intermolecular hydrogen bonding. Overall, the study demonstrated that PEG/Fe3O4 can potentially be used as an efficient control against MPs, thus improving the quality of the aquatic environment and of our water resources.