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Effect of biochar on soil microbial community, dissipation and uptake of chlorpyrifos and atrazine 生物炭对土壤微生物群落、毒死蜱和阿特拉津的消散和吸收的影响
IF 12.7 2区 环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES Pub Date : 2024-03-01 DOI: 10.1007/s42773-024-00306-5
Raghvendra Pratap Singh, Ranu Yadav, Versha Pandey, Anupama Singh, Mayank Singh, Karuna Shanker, Puja Khare

For the application of biochar in restoring pesticide-contaminated soils and minimizing the risk associated with their uptake in plants, it is crucial to understand the biochar impact on soil biological activities and dissipation and accumulation of pesticides in plant and soil systems. In this study, the effect of Mentha-distilled waste-derived biochar was investigated on chlorpyrifos and atrazine contaminated sandy loam soil. The four application rates of atrazine (2, 4, 6, and 8 mg kg−1) and chlorpyrifos (2, 4, 6, and 12 mg kg−1) and a single application rate of biochar (4%) were used in this study. The degradation of pesticides, the diversity of the bacterial community, and enzymatic activities (alkaline phosphatase, dehydrogenase, arylsulfatase, phenol oxidase, urease activity and N-acetyl glucosaminidase) were examined in soil. The uptake of two pesticides and their effect on growth and stress parameters were also investigated in plants (A. paniculata). The dissipation of chlorpyrifos and atrazine followed simple first-order kinetics with a half-life of 6.6–74.6 and 21–145 days, respectively. The presence of deisopropyl atrazine desethyl atrazine (metabolites of atrazine) and 3,5,6-trichloro-2-pyridinol (a metabolite of chlorpyrifos) was observed in soil and plant tissues. Biochar application significantly (p = 0.001) enhanced the degradation rate of chlorpyrifos and atrazine leading to the lower half-life of chlorpyrifos and atrazine in soil. A significant reduction (p = 0.001) in the uptake of chlorpyrifos and atrazine and alteration in their binding affinity and uptake rate in plant tissues was observed in biochar treatments. The incorporation of biochar improved chlorpyrifos/atrazine degrader and plant growth-promoting bacterial genera such as Balneimonas, Kaistobacter, Rubrobacter, Ammoniphilus, and Bacillus. The upregulation of functional genes associated with nucleotide, energy, carbohydrate, amino acid metabolism, xenobiotic biodegradation, and metabolism: atrazine degradation was observed in biochar treatments. The biochar amendments significantly (p = 0.001) reduced the plant’s uptake velocity (Vmax) and affinity (Km) of chlorpyrifos and atrazine. These results delineated that Mentha-distilled waste-derived biochar can potentially remediate chlorpyrifos and atrazine contaminated soils and ensure the safety of plants for consumption.

Graphical Abstract

为了应用生物炭修复受农药污染的土壤,并最大限度地降低植物吸收农药的风险,了解生物炭对土壤生物活动的影响以及农药在植物和土壤系统中的消散和积累至关重要。本研究调查了从薄荷蒸馏废物中提取的生物炭对毒死蜱和阿特拉津污染的砂壤土的影响。本研究采用了阿特拉津(2、4、6 和 8 mg kg-1)和毒死蜱(2、4、6 和 12 mg kg-1)的四种施用量以及生物炭的单一施用量(4%)。研究考察了土壤中农药的降解、细菌群落的多样性和酶活性(碱性磷酸酶、脱氢酶、芳基硫酸酯酶、酚氧化酶、脲酶活性和 N-乙酰氨基葡萄糖酶)。此外,还研究了植物(A. paniculata)对两种农药的吸收及其对生长和胁迫参数的影响。毒死蜱和阿特拉津的消散遵循简单的一阶动力学,半衰期分别为 6.6-74.6 天和 21-145 天。在土壤和植物组织中观察到了脱异丙基阿特拉津、脱乙基阿特拉津(阿特拉津的代谢物)和 3,5,6-三氯-2-吡啶醇(毒死蜱的代谢物)。生物炭的施用大大提高了毒死蜱和阿特拉津的降解率(p = 0.001),从而降低了毒死蜱和阿特拉津在土壤中的半衰期。在生物炭处理中,毒死蜱和阿特拉津的吸收量明显减少(p = 0.001),其在植物组织中的结合亲和力和吸收率也发生了变化。生物炭的加入改善了毒死蜱/莠去津降解菌和植物生长促进菌属,如 Balneimonas、Kaistobacter、Rubrobacter、Ammoniphilus 和 Bacillus。在生物炭处理中观察到与核苷酸、能量、碳水化合物、氨基酸代谢、异生物降解和代谢:阿特拉津降解相关的功能基因上调。生物炭添加剂明显(p = 0.001)降低了植物对毒死蜱和阿特拉津的吸收速度(Vmax)和亲和力(Km)。这些结果表明,从薄荷蒸馏废物中提取的生物炭有可能修复受毒死蜱和阿特拉津污染的土壤,并确保植物的食用安全。
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引用次数: 0
A novel intelligent system based on machine learning for hydrochar multi-target prediction from the hydrothermal carbonization of biomass 基于机器学习的新型智能系统,用于生物质水热碳化过程中水炭多目标预测
IF 12.7 2区 环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES Pub Date : 2024-03-01 DOI: 10.1007/s42773-024-00303-8

Abstract

Hydrothermal carbonization (HTC) is a thermochemical conversion technology to produce hydrochar from wet biomass without drying, but it is time-consuming and expensive to experimentally determine the optimal HTC operational conditions of specific biomass to produce desired hydrochar. Therefore, a machine learning (ML) approach was used to predict and optimize hydrochar properties. Specifically, biochemical components (proteins, lipids, and carbohydrates) of biomass were predicted and analyzed first via elementary composition. Then, accurate single-biomass (no mixture) based ML multi-target models (average R2 = 0.93 and RMSE = 2.36) were built to predict and optimize the hydrochar properties (yield, elemental composition, elemental atomic ratio, and higher heating value). Biomass composition (elemental and biochemical), proximate analyses, and HTC conditions were inputs herein. Interpretation of the model results showed that ash, temperature, and the N and C content of biomass were the most critical factors affecting the hydrochar properties, and that the relative importance of biochemical composition (25%) for the hydrochar was higher than that of operating conditions (19%). Finally, an intelligent system was constructed based on a multi-target model, verified by applying it to predict the atomic ratios (N/C, O/C, and H/C). It could also be extended to optimize hydrochar production from the HTC of single-biomass samples with experimental validation and to predict hydrochar from the co-HTC of mixed biomass samples reported in the literature. This study advances the field by integrating predictive modeling, intelligent systems, and mechanistic insights, offering a holistic approach to the precise control and optimization of hydrochar production through HTC.

Graphical Abstract

摘要 水热碳化(HTC)是一种无需干燥即可从湿生物质中产生水炭的热化学转化技术,但要通过实验确定特定生物质的最佳 HTC 操作条件以产生所需的水炭,既费时又费钱。因此,我们采用了机器学习(ML)方法来预测和优化水炭特性。具体来说,首先通过基本成分预测和分析生物质的生化成分(蛋白质、脂类和碳水化合物)。然后,建立基于单一生物质(无混合物)的精确 ML 多目标模型(平均 R2 = 0.93,RMSE = 2.36),以预测和优化水煤碳特性(产量、元素组成、元素原子比和较高热值)。这里输入了生物质成分(元素和生化)、近似分析和 HTC 条件。对模型结果的解释表明,灰分、温度以及生物质中的氮和碳含量是影响水煤炭特性的最关键因素,而生化成分(25%)对水煤炭的相对重要性高于操作条件(19%)。最后,基于多目标模型构建了一个智能系统,并通过应用该系统预测原子比(N/C、O/C 和 H/C)进行了验证。通过实验验证,该系统还可扩展用于优化单一生物质样品 HTC 产生的炭化水,以及预测文献中报道的混合生物质样品共 HTC 产生的炭化水。本研究通过整合预测建模、智能系统和机理见解,为精确控制和优化通过 HTC 生产水炭提供了一种整体方法,从而推动了该领域的发展。 图表摘要
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引用次数: 0
Microbial mechanisms of organic matter mineralization induced by straw in biochar-amended paddy soil 生物炭改良水稻土中秸秆诱导有机物矿化的微生物机理
IF 12.7 2区 环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES Pub Date : 2024-03-01 DOI: 10.1007/s42773-024-00312-7
Qi Liu, Cuiyan Wu, Liang Wei, Shuang Wang, Yangwu Deng, Wenli Ling, Wu Xiang, Yakov Kuzyakov, Zhenke Zhu, Tida Ge

Combined straw and straw-derived biochar input is commonly applied by farmland management in low-fertility soils. Although straw return increases soil organic matter (SOM) contents, it also primes SOM mineralization. The mechanisms by which active microorganisms mineralize SOM and the underlying factors remain unclear for such soils. To address these issues, paddy soil was amended with 13C-labeled straw, with and without biochar (BC) or ferrihydrite (Fh), and incubated for 70 days under flooded conditions. Compound-specific 13C analysis of phospholipid fatty acids (13C-PLFAs) allowed us to identify active microbial communities utilizing the 13C-labeled straw and specific groups involved in SOM mineralization. Cumulative SOM mineralization increased by 61% and 27% in soils amended with Straw + BC and Straw + Fh + BC, respectively, compared to that with straw only. The total PLFA content was independent of the straw and biochar input. However, 13C-PLFAs contents increased by 35–82% after biochar addition, reflecting accelerated microbial turnover. Compared to that in soils without biochar addition, those with biochar had an altered microbial community composition-increased amounts of 13C-labeled gram-positive bacteria (13C-Gram +) and fungi, which were the main active microorganisms mineralizing SOM. Microbial reproduction and growth were susceptible to nutrient availability. 13C-Gram + and 13C-fungi increased with Olsen P but decreased with dissolved organic carbon and ({text{NO}}_{3}^{ - }) contents. In conclusion, biochar acts as an electron shuttle, stimulates iron reduction, and releases organic carbon from soil minerals, which in turn increases SOM mineralization. Gram + and fungi were involved in straw decomposition in response to biochar application and responsible for SOM mineralization.

Graphical Abstract

在低肥力土壤的农田管理中,通常会使用秸秆和秸秆衍生生物炭的组合投入。虽然秸秆还田增加了土壤有机质(SOM)含量,但同时也促进了 SOM 矿化。活性微生物矿化 SOM 的机制以及这些土壤的基本因素仍不清楚。为了解决这些问题,在水稻田土壤中添加或不添加生物炭(BC)或铁酸盐(Fh),并用 13C 标记的秸秆进行改良,然后在淹水条件下培养 70 天。通过对磷脂脂肪酸(13C-PLFAs)进行特定化合物 13C 分析,我们确定了利用 13C 标记秸秆的活跃微生物群落以及参与 SOM 矿化的特定群落。与仅使用秸秆相比,使用秸秆 + BC 和秸秆 + Fh + BC 改良土壤的累积 SOM 矿化率分别提高了 61% 和 27%。总的 PLFA 含量与秸秆和生物炭的投入量无关。然而,加入生物炭后,13C-PLFAs 的含量增加了 35-82%,这反映了微生物周转的加速。与未添加生物炭的土壤相比,添加了生物炭的土壤的微生物群落组成发生了改变--13C 标记的革兰氏阳性细菌(13C-革兰氏阳性)和真菌的数量增加,它们是矿化 SOM 的主要活性微生物。微生物的繁殖和生长易受养分供应的影响。13C-Gram + 和 13C 真菌随奥尔森 P 的增加而增加,但随溶解有机碳和({text{NO}}_{3}^{ - } )含量的增加而减少。总之,生物炭充当了电子穿梭器的角色,刺激铁还原,并从土壤矿物中释放有机碳,这反过来又增加了 SOM 的矿化。革兰氏+和真菌参与了施用生物炭后的秸秆分解,并负责SOM的矿化。
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引用次数: 0
Potentials of emergent plant residue derived biochar to be alternative carbon-based phosphorus fertilizer by Fe(II)/Fe(III) magnetic modification 通过铁(II)/铁(III)磁性改性使新兴植物残留物衍生生物炭成为替代碳基磷肥的潜力
IF 12.7 2区 环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES Pub Date : 2024-02-26 DOI: 10.1007/s42773-024-00300-x
Hongjuan Xin, Jiao Yang, Yuanyuan Lu, Hekang Xiao, Haitao Wang, Kamel M. Eltohamy, Xueqi Zhu, Chunlong Liu, Yunying Fang, Ye Ye, Xinqiang Liang

Emergent plants have been remarkably effective in reducing phosphorus (P) discharge from ecological ditches; however, the treatment and recycling of these residues is a great challenge. In this study, magnetic biochars (MBs, i.e., MB-A, MB-C, and MB-T) were fabricated from three emergent plant residues (Acorus calamus L., Canna indica L., and Thalia dealbata Fraser, respectively) and modified with Fe(II)/Fe(III). Scanning electron microscopy-energy dispersive spectroscopy and X-ray diffraction spectra confirmed the successful loading of Fe3O4 and FeO(OH) onto the surfaces of the MBs. Batch adsorption experiments showed that MBs exhibited a higher P adsorption capacity than that of the raw biochars. Within the range of 0.8–43.0 mg L−1 in solution, the adsorption capacities of P by MB-A, MB-C, and MB-T were 304.6–5658.8, 314.9–6845.6, and 292.8–5590.0 mg kg−1, with adsorption efficiencies of 95.2–32.9%, 98.4–39.8%, and 91.5–32.5%, respectively. The primary mechanisms that caused P to adsorb onto the MBs were inner-sphere complexation and electrostatic attraction. Low pH conditions were more beneficial for the P adsorption of the MBs, while co-existing anions had a negative impact with the following order: HCO3 > SO42− > Cl≈NO3. The P-31 nuclear magnetic resonance results further demonstrated that the main adsorbed P species on the MBs was orthophosphate, followed by orthophosphate monoesters and DNA. Overall, MBs offer a resource utilization strategy for emergent plant residues and P-laden MBs are promising alternative P fertilizers.

Graphical Abstract

新生植物在减少生态沟渠磷排放方面效果显著;然而,这些残留物的处理和回收利用是一项巨大的挑战。在这项研究中,磁性生物炭(MBs,即 MB-A、MB-C 和 MB-T)是由三种新兴植物残留物(分别为石菖蒲、石菖蒲和 Thalia dealbata Fraser)制成,并用铁(II)/铁(III)进行改性。扫描电子显微镜-能量色散光谱和 X 射线衍射光谱证实,Fe3O4 和 FeO(OH) 成功地负载到了 MBs 的表面。批量吸附实验表明,甲基溴对 P 的吸附能力高于未加工的生物沥青。在 0.8-43.0 mg L-1 的溶液范围内,MB-A、MB-C 和 MB-T 对 P 的吸附容量分别为 304.6-5658.8、314.9-6845.6 和 292.8-5590.0 mg kg-1,吸附效率分别为 95.2-32.9%、98.4-39.8% 和 91.5-32.5%。使 P 吸附到甲基溴上的主要机制是内球络合和静电吸引。HCO3- > SO42- > Cl-≈NO3-.P-31 核磁共振结果进一步表明,甲基溴上主要吸附的 P 物种是正磷酸盐,其次是正磷酸盐单酯和 DNA。总之,甲基溴为新兴植物残留物提供了一种资源利用策略,含磷甲基溴是一种很有前景的替代性磷肥。
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引用次数: 0
Biochar application regulating soil inorganic nitrogen and organic carbon content in cropland in the Central Europe: a seven-year field study 应用生物炭调节中欧耕地土壤中的无机氮和有机碳含量:一项为期七年的实地研究
IF 12.7 2区 环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES Pub Date : 2024-02-22 DOI: 10.1007/s42773-024-00307-4
Narges Hematimatin, Dušan Igaz, Elena Aydın, Ján Horák

Biochar incorporation into soil has shown potential, in enhancing nitrogen fertilizer (N-fertilizer) efficacy and soil organic carbon content (SOC). This study addresses a critical gap in the literature by investigating the effects of biochar addition over a seven-year period (2014–2020) on inorganic N, SOC, and pH in Haplic Luvisol. The research involved a rain-fed field experiment, with a crop rotation comprising spring barley, maize, spring wheat, and pea. Biochar, applied at the rates of 0, 10, and 20 t ha−1 in 2014, was reapplied to specific plots in 2018. Biochar was also combined with N-fertilizer at three level (N0, N1, and N2). Results showed a significant interactive influence of biochar and N-fertilizer combination on NO3 and NH4+ contents. Intriguingly, the addition of 10 t biochar ha−1 consistently decreased soil inorganic N levels across most of the examined months. Increasing biochar application rates led to a significant rise in pH, establishing a clear, negative correlation between soil pH and inorganic N content. Biochar significantly increased SOC compared to the control, particularly after the reapplication in 2018. However, this effect showed a diminishing trend over time. The study suggests that incorporating biochar treatments may enhance N-fertilizer effectiveness. However, the long-term implications of biochar application with N-fertilizer on N mineralization are specific to individual soil and biochar combinations. Except the application of 20 t ha−1 biochar at N2 in 2019, biochar did not affect the crop yields. Studied soil properties, including those influenced by biochar had nuanced impact on different aspects of crop yield.

Graphical Abstract

将生物炭掺入土壤具有提高氮肥(N-肥)功效和土壤有机碳含量(SOC)的潜力。本研究针对文献中的一个重要空白,调查了在七年期间(2014-2020 年)添加生物炭对 Haplic Luvisol 中无机氮、SOC 和 pH 值的影响。研究涉及一项雨水灌溉田间试验,作物轮作包括春大麦、玉米、春小麦和豌豆。生物炭在2014年的施用量分别为0、10和20吨/公顷,2018年再次施用到特定地块。生物炭还与氮肥在三个水平(N0、N1 和 N2)上结合使用。结果表明,生物炭与氮肥的组合对 NO3- 和 NH4+ 的含量有明显的交互影响。耐人寻味的是,在大部分考察月份中,每公顷添加 10 吨生物炭会持续降低土壤中的无机氮含量。生物炭施用量的增加导致 pH 值显著上升,从而在土壤 pH 值和无机氮含量之间建立了明确的负相关关系。与对照组相比,生物炭明显增加了 SOC,尤其是在 2018 年再次施用后。然而,随着时间的推移,这种效果呈递减趋势。研究表明,加入生物炭处理可提高氮肥的效果。然而,生物炭与氮肥一起施用对氮矿化的长期影响取决于不同的土壤和生物炭组合。除了 2019 年在 N2 条件下施用 20 吨/公顷生物炭外,生物炭并未影响作物产量。所研究的土壤特性,包括受生物炭影响的土壤特性,对作物产量的不同方面有着细微的影响。
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引用次数: 0
Reduced sulfur compounds and carboxylic acid groups in dissolved PFRs of iron-biochar enhance Cr(VI) reduction in anaerobic conditions 铁生物炭溶解的全氟膦酸中的还原硫化合物和羧酸基团可提高厌氧条件下的六价铬还原能力
IF 12.7 2区 环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES Pub Date : 2024-02-20 DOI: 10.1007/s42773-024-00305-6
Shujie Hu, Chengshuai Liu, Hongling Bu, Manjia Chen, Jiao Tang, Bin Jiang, Yong Ran

In addition to the adsorption and immobilization capacities of iron-modified biochars, these materials produce persistent free radicals (PFRs) that can carry out metal [i.e., Cr(VI)] redox transformations, but the primary forms and active species of PFRs involved are not well understood. Here, we investigated the key species of PFRs of α-Fe2O3-modified biochar (MBC) and their influence on Cr(VI) reduction under anaerobic conditions simulating paddy soil environments. MBC produced bulk phenoxyl PFRs that promoted Cr(VI) reduction due to the catalytic effect of the transition metal Fe. In addition, MBC was more efficient in reducing Cr(VI) under anaerobic conditions than under aerobic conditions due to the more active and accessible dissolved PFRs present in the dissolved organic matter (DOM). The electron transfer capacity of DOM was demonstrated by excitation-emission matrix (EEM) spectrophotometry combined with parallel factor analysis, which showed that the protein-like and humic-like components of DOM were involved in Cr(VI) reduction. Furthermore, Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) analysis indicated that reduced-S compounds (O/S < 4) and carboxylic acid (–COO) groups in the unsaturated aliphatic and lignin-like compounds are potentially the main active species accelerating Cr(VI) reduction under anaerobic conditions. Our results provide new insights into the role of dissolved PFRs from iron-modified biochar in promoting Cr(VI) reduction under anaerobic conditions such as flooded soils.

Graphical Abstract

除了铁改性生物炭的吸附和固定能力之外,这些材料还会产生持久性自由基(PFR),这些自由基可以进行金属[即六价铬]的氧化还原转化,但目前还不太清楚其中涉及的持久性自由基的主要形式和活性物种。在此,我们研究了α-Fe2O3 改性生物炭(MBC)中的主要 PFR 物种及其在模拟水稻田土壤环境的厌氧条件下对 Cr(VI) 还原的影响。由于过渡金属 Fe 的催化作用,MBC 产生的大量苯氧基全氟辛基磺酰氟促进了六(Cr)的还原。此外,在厌氧条件下,由于溶解有机物(DOM)中存在更活跃、更易获取的溶解性全氟辛基磺酰氟,因此与好氧条件相比,MBC 在厌氧条件下还原六价铬的效率更高。激发-发射矩阵(EEM)分光光度法结合平行因子分析证明了 DOM 的电子传递能力,结果表明 DOM 中的蛋白质类和腐殖质类成分参与了六(VI)铬的还原。此外,傅立叶变换离子回旋共振质谱(FTICR-MS)分析表明,不饱和脂肪族和木质素类化合物中的还原-S化合物(O/S < 4)和羧酸(-COO)基团可能是厌氧条件下加速六价铬还原的主要活性物种。我们的研究结果为了解铁改性生物炭中溶解的全氟膦酸在厌氧条件下(如水淹土壤)促进六价铬还原的作用提供了新的视角。
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引用次数: 0
Standardization and micromechanistic study of tetracycline adsorption by biochar 生物炭吸附四环素的标准化和微观机理研究
IF 12.7 2区 环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES Pub Date : 2024-02-06 DOI: 10.1007/s42773-023-00299-7
Xiaotong Zhang, Jinju Hou, Shudong Zhang, Tong Cai, Shujia Liu, Wenjin Hu, Qiuzhuo Zhang

Modification serves as an excellent approach to enhancing the adsorption performance of biochar for tetracycline. Selective modification further allows the attainment of biochar materials that are not only more efficient but also cost-effective. However, the key structural factors influencing the adsorption of tetracycline by biochar remain unclear at present, hindering the effective guidance for modification strategies. This study established the relationship between carbonization degree and adsorption capacity, constructed a standardized microscopic model for biochar adsorption of tetracycline, and explored potential reaction mechanisms. The results indicated that with increases in the degree of carbonization, the tetracycline adsorption capacity of biochar increased from 16.08 mg L−1 to 98.35 mg L−1. The adsorption energy exhibited a strong correlation with the aromatic condensation of biochar at p ≤ 0.01, with a linear relationship (r2 ≥ 0.94). For low carbonization degrees, the adsorption of tetracycline by biochar was primarily driven by chemical bonds (69.21%) and complemented with electrostatic interactions, weak van der Waals forces or π-π interactions. For high carbonization degrees, the synergistic effects of hydrogen bonding, van der Waals forces, and π-π interactions determined the adsorption of tetracycline on biochar (91.1%). Additionally, larger carbon clusters resulted in stronger and more stable adsorption interactions. Furthermore, carboxyl-functionalized highly carbonized biochar displayed the highest reaction energy of − 1.8370 eV for adsorption of tetracycline through electrostatic interactions. This study suggests that a high degree of aromatic condensation in the carbon structure of biochar is crucial for the efficient adsorption of tetracycline.

Graphical Abstract

改性是提高生物炭对四环素吸附性能的绝佳方法。选择性改性还可进一步获得不仅更高效,而且成本效益更高的生物炭材料。然而,目前影响生物炭吸附四环素的关键结构因素仍不明确,阻碍了对改性策略的有效指导。本研究确定了碳化程度与吸附容量之间的关系,构建了生物炭吸附四环素的标准化微观模型,并探讨了潜在的反应机理。结果表明,随着碳化程度的增加,生物炭的四环素吸附容量从 16.08 mg L-1 增加到 98.35 mg L-1。在 p ≤ 0.01 时,吸附能与生物炭的芳香缩合度呈线性关系(r2 ≥ 0.94)。低碳化度时,生物炭对四环素的吸附主要由化学键驱动(69.21%),并辅以静电作用、弱范德华力或 π-π 作用。在碳化程度较高的情况下,氢键、范德华力和π-π相互作用的协同效应决定了四环素在生物炭上的吸附率(91.1%)。此外,较大的碳簇可产生更强、更稳定的吸附相互作用。此外,羧基官能化的高碳化生物炭通过静电作用吸附四环素的反应能量最高,为 - 1.8370 eV。这项研究表明,生物炭碳结构中高度的芳香缩合是高效吸附四环素的关键。
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引用次数: 0
Preparation of biochar adsorption material from walnut shell by supercritical CO2 pretreatment 用超临界二氧化碳预处理制备核桃壳生物炭吸附材料
IF 12.7 2区 环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES Pub Date : 2024-01-26 DOI: 10.1007/s42773-024-00302-9
Zitong Zhuang, Yanbing Liu, Wenwen Wei, Jinwen Shi, Hui Jin

In order to treat dyes in the wastewater of the printing industry and to reutilize walnut shell (WS) waste generate economic benefits, supercritical carbon dioxide (SC-CO2) pretreatment technology was developed to prepare porous biochar as a precursor for adsorption material. Orthogonal experiments were conducted at the temperatures of 200, 300, and 400 ℃ with durations of 20, 40, and 60 min, and a control group was set up using N2 pretreatment. Then, KOH activation was employed to prepare biochar adsorption material. The biochars were analyzed and characterized using TGA, BET, SEM, FT-IR, and XRD, and the liquid and gas phase products of the pretreatment process were analyzed semi-quantitatively and quantitatively using GC–MS and gas chromatography. Methylene blue (MB) dye was selected as an indicator to measure the adsorption capacity of biochar, and adsorption kinetics were analyzed based on the data. The results indicate that pretreatment with SC-CO2 effectively enhanced the performance and yield of the activated carbon. The highest specific surface area increased by 18%, and the maximum adsorption of MB increased by 23% compared to the N2 control group. The yield increased by 8–262% and the specific surface area increased by 50–192% compared to the direct activation of walnut shell (WS). During the pretreatment processes for the preparation of biochar adsorption material with the best specific surface area, phenol-enriched bio-oil was produced as a by-product which has economic value.

Graphical Abstract

为了处理印刷业废水中的染料,并使核桃壳(WS)废料再利用产生经济效益,研究人员开发了超临界二氧化碳(SC-CO2)预处理技术,以制备多孔生物炭作为吸附材料的前驱体。实验温度分别为 200、300 和 400 ℃,持续时间分别为 20、40 和 60 分钟。然后,采用 KOH 活化法制备生物炭吸附材料。利用 TGA、BET、SEM、FT-IR 和 XRD 对生物炭进行了分析和表征,并利用 GC-MS 和气相色谱法对预处理过程中的液相和气相产物进行了半定量和定量分析。选择亚甲基蓝(MB)染料作为衡量生物炭吸附能力的指标,并根据数据分析了吸附动力学。结果表明,用 SC-CO2 进行预处理可有效提高活性炭的性能和产量。与 N2 对照组相比,最高比表面积增加了 18%,甲基溴的最大吸附量增加了 23%。与直接活化核桃壳(WS)相比,产量增加了 8-262%,比表面积增加了 50-192%。在制备具有最佳比表面积的生物炭吸附材料的预处理过程中,产生了富含酚的生物油作为副产品,具有经济价值。
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引用次数: 0
Machine learning insights in predicting heavy metals interaction with biochar 预测重金属与生物炭相互作用的机器学习见解
IF 12.7 2区 环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES Pub Date : 2024-01-25 DOI: 10.1007/s42773-024-00304-7

Abstract

The use of machine learning (ML) in the field of predicting heavy metals interaction with biochar is a promising field of research, mainly because of the growing understanding of how removal efficiency is affected by characteristic variables, reaction conditions and biochar properties. The practical application in biochar still faces large challenges, such as difficulties in data collection, inadequate algorithm development, and insufficient information. However, the quantity, quality, and representation of data have a large impact on the accuracy, efficiency, and generalizability of machine learning tasks. From this perspective, the present data descriptors, the efficiency of machine learning-aided property and performance prediction, the interpretation of underlying mechanisms and complicated relationships, and some potential ways to augment the data are discussed regarding the interactions of heavy metals with biochar. Finally, future perspectives and challenges are discussed, and an enhanced model performance is proposed to reinforce the feasibility of a particular perspective.

Graphical Abstract

摘要 机器学习(ML)在预测重金属与生物炭相互作用领域的应用是一个前景广阔的研究领域,这主要是因为人们对去除效率如何受特征变量、反应条件和生物炭特性的影响有了越来越多的了解。生物炭的实际应用仍然面临着巨大的挑战,如数据收集困难、算法开发不足、信息不充分等。然而,数据的数量、质量和代表性对机器学习任务的准确性、效率和可推广性有很大影响。从这个角度出发,讨论了有关重金属与生物炭相互作用的现有数据描述符、机器学习辅助属性和性能预测的效率、潜在机制和复杂关系的解释,以及一些潜在的增强数据的方法。最后,讨论了未来的前景和挑战,并提出了增强模型性能的建议,以加强特定观点的可行性。 图表摘要
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引用次数: 0
Synergistically enhancing nitrate reduction into N2 in water by N-doped Pd–Cu biochar bimetallic single-atom electrocatalysis 掺杂 N 的 Pd-Cu 生物炭双金属单原子电催化协同提高水中硝酸盐还原成 N2 的能力
IF 12.7 2区 环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES Pub Date : 2024-01-15 DOI: 10.1007/s42773-023-00298-8
Lihao Zhang, Yuqing Wu, Zongqiang Zhu, Yinian Zhu, Yi Dong, Meina Liang, Huan Deng

Noble metal materials have been identified as high efficiency catalysts for electrocatalytic reduction of nitrate, and the synthesis and manufacture of high catalytic activity and environmentally friendly catalysts of activating hydrogen for water purification applications is extremely attractive. In this work, the Pd–Cu single-atom catalysts (Pd–Cu-N-BC) were first prepared by direct growth of Pd–Cu single-atom on bamboo biochar by regulating the concentration of precursors and doping method, and then enhanced electrocatalytic reduction nitrate performance and N2 generation. The results showed that Pd–Cu-N-BC displayed excellent catalytic activity and reusability in electrocatalytic reduction nitrate with a low potential of 0.47 V vs. RHE (@10 mA cm−2). The maximum nitrate removal efficiency and N2 generation could reach about 100% and 72.32% within 180 min, respectively. The density functional theory (DFT) calculations confirmed that Cu atoms could catalyze the electrochemical reduction of nitrate to nitrite, and Pd atoms anchored in the nitrogen-doped biochar (N-BC) lattice could catalyze electrochemical reduction of nitrite to N2 involving the formation of hydrogen radical (H*). The characterization results of XANES showed that electronic synergistic effect between Pd and Cu single atoms significantly promotes the N2 production through hydrogenation while inhibiting the generation of byproducts, leading to significantly enhanced electrocatalytic reduction of nitrate to N2. Finally, Pd–Cu-N-BC was designed as a 3D particle electrode for enhanced electrocatalytic reduction of nitrate, exhibiting excellent stability and reusability, which could be considered as a suitable candidate for applications in the remediation of nitrate contamination.

Graphical Abstract

贵金属材料已被确认为硝酸盐电催化还原的高效催化剂,而合成和制造高催化活性和环境友好的活化氢催化剂用于水净化应用则极具吸引力。本研究首先通过调节前驱体浓度和掺杂方法,在竹生物炭上直接生长 Pd-Cu 单原子,制备了 Pd-Cu 单原子催化剂(Pd-Cu-N-BC),进而增强了电催化还原硝酸盐的性能和 N2 的生成。结果表明,Pd-Cu-N-BC 在电催化还原硝酸盐中表现出优异的催化活性和可重复使用性,对 RHE 的低电位为 0.47 V(@10 mA cm-2)。在 180 分钟内,硝酸盐的最大去除率和 N2 的最大生成率分别达到约 100%和 72.32%。密度泛函理论(DFT)计算证实,Cu 原子可催化硝酸盐电化学还原为亚硝酸盐,而锚定在掺氮生物炭(N-BC)晶格中的 Pd 原子可催化亚硝酸盐电化学还原为 N2,其中涉及氢自由基(H*)的形成。XANES 表征结果表明,Pd 和 Cu 单原子之间的电子协同效应显著促进了通过氢化产生 N2,同时抑制了副产物的生成,从而显著增强了将硝酸盐电催化还原为 N2 的能力。最后,Pd-Cu-N-BC 被设计成一种用于增强硝酸盐电催化还原的三维颗粒电极,表现出优异的稳定性和可重复使用性,可作为硝酸盐污染修复应用的合适候选材料。 图文摘要
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引用次数: 0
期刊
Biochar
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