Biochar-derived Dissolved Organic Matter Research Articles

Biochar-derived dissolved organic matter enhanced the release of residual ciprofloxacin from the soil solid phase

Biochar has been utilized to reduce ciprofloxacin (CIP) residues in soil. However, little is known about the effect of biochar-derived dissolved organic matter (DOM) on residual CIP transformation. Thus, we analyzed the residual soil CIP as influenced by biochar generated from rice straw (RS3 and RS6), pig manure (PM3 and PM6), and cockroach shell (CS3 and CS6) at 300 °C and 600 °C. The three-dimensional excitation-emission matrix (3D-EEM), parallel factor analysis (PARAFAC) and two-dimensional correlation spectral analysis (2D-COS) were used to describe the potential variation in the DOM-CIP interaction. Compared with CK, biochar amendment increased the water-soluble CIP content by 160.7% (RS3), 55.2% (RS6), 534.1% (PM3), 277.5% (PM6), 1160.6% (CS3) and 703.9% (CS6), indicating that the biochar feedstock controlled the soil CIP release. The content of water-soluble CIP was positively correlated with the content of dissolved organic carbon (r = 0.922, p < 0.01) and dissolved organic nitrogen (r = 0.898, p < 0.01), suggesting that the major influence of the water-soluble CIP increase was DOM. The fluorescence quenching experiment showed that the interaction between DOM and CIP triggered static quenching and the creation of a DOM complex. The mean log K of protein-like material (4.977) was higher than that of terrestrial humus-like material (3.491), suggesting that the protein-like material complexed CIP was more stable than the humus-like material. Compared with pyrolysis at 300 °C, pyrolysis at 600 °C decreased the stability of the complex of protein-like material and CIP by 0.44 (RS), 1.689 (PM) and 0.548 (CS). This result suggested that the influence of temperature change was more profound on PM biochar-derived DOM than on RS and CS. These insights are essential for understanding CIP transportation in soil and controlling CIP contamination with biochar.

Spectroscopic insights into the influence of oxidation on the binding properties of Cu(II) onto biochar-derived dissolved organic matter

The oxidation may change the composition, content, and structure of biochar-derived dissolved organic matter (BDOM) that influences the geochemical behavior of heavy metals (HMs) when biochar is applied. Herein, the binding characteristics of Cu(II) onto BDOM and oxidized BDOM (OBDOM) were investigated using synchronous fluorescence spectra (SFS) and Fourier transform infrared (FTIR) spectroscopy in combination with two-dimensional correlation spectroscopy (2D-COS). The results showed that the content of BDOM300 and BDOM600 decreased by 30.21% and 13.67% respectively after oxidation. Humic-like substances are dominated in the BDOM, which can be preferentially oxidized. Meanwhile, humic-like substances (e.g. 412 nm in the BDOM300, 490 nm in the OBDOM300, 525 nm in the BDOM600, and OBDOM600) can preferentially react with Cu(II). The functional groups, at 1712 cm−1 in the BDOM300, 1631 and 1290 cm−1 in the OBDOM300, 1515 cm−1 in the BDOM600, 1740 cm−1 in the OBDOM600, played important roles in the complexation between humic-like substances and Cu(II). The logarithmic conditional stability constant (Log K) of the complexes is higher in the OBDOM300 than those in the BDOM300, and higher in the OBDOM600 than those in the BDOM600. The results also indicated that the presence of BDOM promoted the adsorption of Cu(II) by BC300 and BC600, and inhibited the adsorption of Cu(II) by OBC300 and OBC600. Therefore, it is particularly important to insight into the effect of oxidation on the binding properties of Cu(II) and BDOM. This study can provide scientific guidance for the use of biochar in the remediation of HMs.

Effect of pyrolysis temperature on the binding characteristics of DOM derived from livestock manure biochar with Cu(II).

Biochar-derived dissolved organic matter (BDOM) has the potential to influence the environmental application of biochar and the behavior of heavy metals. In this study, the binding properties of BDOM derived from livestock manure biochar at different pyrolysis temperatures with Cu(II) were investigated based on a multi-analytical approach. The results showed that the DOC concentration, aromatics, and humification degree of BDOM were higher in the process of low pyrolysis of biochar. The pyrolysis temperature changed the composition of BDOM functional groups, which affected the binding mechanism of BDOM-Cu(II). Briefly, humic-like and protein-like substances dominated BDOM-Cu(II) binding at low and high pyrolysis temperatures, respectively. The higher binding capacity for Cu(II) was exhibited by BDOM derived from the lower pyrolysis temperature, due to the carboxyl as the main binding site in humic acid had high content and binding ability at low-temperature. The amide in proteins only participated in the BDOM-Cu(II) binding at high pyrolysis temperature, and polysaccharides also played an important role in the binding process. Moreover, the biochar underwent the secondary reaction at certain high temperatures, which led to condensation reaction of the aromatic structure and the conversion of large molecules into small molecules, affecting the BDOM-Cu(II) binding sites.

Unveiling the effect of different dissolved organic matter (DOM) on catalytic dechlorination of nFe/Ni particles: Corrosion and passivation effect

Dissolved organic matter (DOM), which is ubiquitously distributed in groundwater, has a crucial role in the fate and reactivity of iron materials. However, there is a lack of direct evidence on how different DOMs interact with nFe/Ni in promoting or inhibiting the dechlorination efficiency of chlorinated aromatic contaminants. By comparing humic acid (HA), fulvic acid (FA), and biochar-derived dissolved organic matter (BDOM) at different pyrolysis temperatures, we first demonstrated that the dechlorination effect of nFe/Ni on 2,4-dichlorophenol (2,4-DCP) depended on the nature of DOMs and their adsorption on nFe/Ni. HA showed an enhancing effect on the dechlorination of 2,4-DCP by nFe/Ni, while the inhibition effect of other DOMs resulted in the following dechlorination order: BDOM300 ≈FA>BDOM700 ≈BDOM500. The C2 component with higher aromaticity and molecular weight promoted the corrosion of nFe/Ni and the production of reactive hydrogen atoms (H*). The effects of different DOMs on nFe/Ni include that (1) HA accelerates the corrosion and H* production of nFe/Ni, (2) FA and BDOM300 enhance the corrosion but inhibit H* production, and (3) Both nFe/Ni corrosion and H* formation are suppressed by BDOM500/BDOM700. Therefore, this study will provide a reference for understanding the nature of DOM-nFe/Ni interaction and improving the catalytic activity of nFe/Ni when different DOMs coexist in practical applications.

Pyrolysis temperature matters: Biochar-derived dissolved organic matter modulates aging behavior and biotoxicity of microplastics

Microplastics (MPs) have emerged as a novel and highly concerning contaminant that is ubiquitous in the aqueous environment. However, the aging of MPs induced by dissolved organic matter (DOM), especially biochar-derived dissolved organic matter (BDOM), and the biological toxicity after aging are not fully understood. In this study, the effects of biochar-derived BDOMs on the photoaging and biotoxicity of MPs were investigated at different pyrolysis temperatures using micro-scale polyethylene (PE) as an example. The results showed that the amount of ·OH generated by the BDOM/PE systems was related to the molecular composition and structure of BDOMs. High temperature BDOM7/9 with less lignin-like (34.33 % / 41.80 %) and more lipid (24.58 % / 19.88 %) content could produce more ·OH by itself, and its binding ability with PE was weaker due to its less hydrophobic components (SUVA260 = 0.10 / 0.11), which resulted in a weaker shading effect and less inhibition of the system, thus resulting in more ·OH production in the high temperature BDOM7/9/PE system. However, the involvement of BDOM, although favoring the long-term stable ·OH production of the system, did not significantly promote the photoaging of MPs. Furthermore, combined in vivo and in vitro biotoxicity studies of MPs showed that photoaging PE with the involvement of BDOM greatly improved systemic inflammation and tissue damage, as well as reactive oxygen species (ROS, such as ·OH and -OH)-induced cell death. For example, the addition of BDOM5/PE-light reduced the cell death of human lung, liver, and kidney cells from 54.70 %, 69.39 %, and 48.35 % to 22.78 %, 33.13 %, and 25.83 %, respectively, compared to the PE-light group. The results of this study contribute to an in-depth understanding of the environmental behavior of BDOM and MPs systems.

Effects of biochar-derived dissolved organic matter on the gut microbiomes and metabolomics in earthworm Eisenia fetida

The ecological risks of biochar-derived dissolved organic matter (DOM) to soil invertebrates at different organismal levels remains limited. This study comprehensively explored the ecological risks of biochar-derived DOM on earthworm gut through assessments of enzyme activity response, histopathology, gut microbiomes, and metabolomics. Results demonstrated that DOM disturbed the digestive enzymes in earthworm, especially for 10% DOM300 groups. The integrated biomarker response v2 (IBRv2) indicated that the perturbation of earthworm digestive enzymes induced by DOM was both time-dependent and dose-dependent. Pathological observations revealed that 10% DOM300 damaged intestinal epithelium and digestive lumen of earthworms. The significant damage and injury to earthworms caused by DOM300 due to its higher concentrations of heavy metal ions and organic substrates (e.g., toluene, hexane, butanamide, and hexanamide) compared to DOM500 and DOM700. Analysis of 16S rRNA from the gut microbiota showed a significant decrease in genera (Verminephrobacter, Bacillus, and Microbacteriaceae) associated with inflammation, disease, and detoxification processes. Furthermore, 10% DOM300 caused the abnormality of metabolites, such as glutamate, fumaric acid, pyruvate, and citric acid, which were involved in energy metabolism, These findings contributed to improve our understanding of the toxic mechanism of biochar DOM from multiple perspectives.

Release of biochar-derived dissolved organic matter and the formation of chlorination disinfection by-products: Effects of pH and chlorine dosage

Transformation, fragmentation, dissolution, and oxidation of biochar are inevitable in the environment, which will undoubtedly accelerate the release of biochar-derived dissolved organic matter (BDOM) into various water bodies. In addition, biochar may affect disinfection by-products (DBPs) during water treatment and subsequent disinfection. In this study, biochars were derived at three selected pyrolysis temperatures (350 °C, 500 °C, and 650 °C) from rice husk, wheat straw, and shrimp shell, and BDOM was extracted from biochar-derived in artificial seawater and ultrapure water. The TOC analyzer results showed that the concentrations of three BDOM decreased with increasing pyrolysis temperature. The BDOM derived from rice husk biochar and wheat straw biochar in seawater was lower than that in ultrapure water, while that of shrimp shell biochar showed an opposite trend, being released in seawater at nearly twice the extent of that in ultrapure water at 350 °C. Moreover, BDOM showed a catalytic effect on chlorination, and GC analysis showed that the concentrations of its DBPs were affected by pH. The concentration of halogenated acetic acid reached the highest value (54.51 μg/L) in weak acidic environment, while the concentrations of trihalomethane and halogenated acetonitrile had the highest values (23.63 and 47.53 μg/L, respectively) in alkaline conditions. The concentrations of all the three DBPs were lowest under neutral pH conditions. In addition, the volatile halogenated DBPs such as dichloroacetone and trichloroacetone were easily hydrolyzed under alkaline conditions. Therefore, it is something be aware of the release of BDOM and the effects of chlorination DBPs when biochar is used for water treatment or water purification.

Inhibition mechanisms of biochar-derived dissolved organic matter to triclosan photodegradation: A remarkable role of aliphatics

Endocrine disrupting chemicals like triclosan (TCS) have been thought to be an emergent environmental pollutant. The ubiquitous dissolved organic matter (DOM) is able to interrelate with TCS and hamper its phototransformation. However, how the components in DOM can inhibit the photodegradation of DOM/TCS complex is largely unknown. Herein, we discovered that TCS photodegradation with biochar-derived DOM (BDOM) was interfered by both binding affinity and reactive oxygen species (ROS) productivity. BDOM can not only stimulate TCS photodegradation by producing ROS, but also inhibit the removal of TCS through the interactions between BDOMs and TCS. The quantification of BDOM's impact on TCS photodegradation revealed that BDOM hampered TCS removal with the proportion of −7.95 to −11.24% at pH 8.5, but strengthened it to 13.20% at pH 7.0. Binding process was more easily to inhibit TCS photodegradation in molecular form, while anionic TCS photodegradation was dominated by ROS productivity. Different inhibition mechanisms were involved in TCS photodegradation depending on the components of BDOMs. The hydroxyls and aromatic carbonyls might have hindered the attack of ROS on the phenolic hydroxyl of TCS via hydrogen bond interaction or π-π electron donor-acceptor interaction. Through hydrophobic interaction, the mobile aliphatics could greatly shield TCS to prevent ROS attack by wrapping or twining TCS, playing a significant role in inhibiting TCS removal. Results from this present study can afford a new viewpoint in elucidating the function of BDOMs in the phototransformation of organics and decrease the spread of antibiotic resistance genes.

Differential influences of forest floor-pyrolyzed biochar-derived and leached dissolved organic matter interaction with natural iron-bearing minerals in forest subsoil on the formation of mineral-associated soil organic matter

The vertical sequestration of dissolved organic matter (DOM) by iron minerals along the soil profile is assumed to be central to the long-term storage of the soil organic matter (SOM) pool. However, there is limited information available about how the interaction between DOM and natural iron-bearing minerals shape mineral SOM associations quantitatively and qualitatively in forest subsoils. Here, we systematically investigated the influences of forest organic layer-pyrolyzed biochar-derived DOM (BDOM) and leached DOM (LDOM) on quantity, molecular composition, and diversity of deposition layer-derived iron minerals-associated OM by using Fourier transform ion cyclotron resonance mass spectrometry and other complementary spectroscopy. Results indicated natural iron minerals (FeOx1 and FeOx2) had a greater capacity for sorbing LDOM with higher aromaticity and molecular weight than those of BDOM, and the higher proportion of goethite and short-order-range phase in natural iron minerals was closely related to the increased OM adsorption capacity. We also observed the preferential sorption of oxygen/nitrogen-rich polycyclic aromatic compounds and carboxylic-containing compounds in LDOM and concurrent the potential release of lignin-like/aromatics compounds and carboxyl/nitrogen-less aliphatic compounds from native OM coprecipitates into the solution. However, unsaturated and oxidized phenolic compounds in BDOM had a stronger affinity for FeOx through hydrophobic partitioning and specific polar interactions, and concomitantly the partial release of nitrogen-free aliphatic and other carboxyl-rich compounds. More nitrogen structures in aromatic-containing compounds can improve the saturation level and polarity of BDOM. Compared with BDOM, LDOM exerted a stronger control over the exchange of native OM from subsoil natural iron-bearing minerals and substantially enhanced the molecular diversity of the reconstituted mineral-associated OM during the adsorptive fractionation. Overall, these findings suggest the compositional evolution of DOM profoundly shapes SOM formation and persistence in forest subsoils, which is the key to understanding DOM cycling and contaminant fate during its passage through the soil.

Systematic assessment of the ecotoxicological effects and mechanisms of biochar-derived dissolved organic matter (DOM) on the earthworm Eisenia fetida

Biochar-derived dissolved organic matter (DOM) contains toxic substances that are first released into the soil after biochar application. However, the ecological risks of biochar-derived DOM on soil invertebrate earthworms are unclear. Therefore, this study investigated the ecological risks and toxic mechanisms of sewage sludge biochar (SSB)-derived DOM on the earthworm Eisenia fetida (E. fetida) via microcosm experiments. DOM exposure induced earthworm death, growth inhibition, and cocoon decline. Moreover, DOM, especially the 10% DOM300 (derived from SSB prepared at 300 °C) treatments, disrupted the antioxidant defense response and lysosomal stability in earthworms. Integrated biomarker response v2 (IBRv2) analysis was performed to assess the comprehensive toxicity of DOM in E. fetida, and the results revealed that DOM300 might exert more hazardous effects on earthworms than DOM500 (prepared at 500 °C) and DOM700 (prepared at 700 °C), as revealed by increases in the IBRv2 value of 3.48–18.21. Transcriptome analysis revealed that 10% DOM300 exposure significantly disrupted carbohydrate and protein digestion and absorption and induced endocrine disorder. Interestingly, 10% DOM300 exposure also significantly downregulated the expression of genes involved in signaling pathways, e.g., the P13K-AKT, cGMP-PKG, and ErbB signaling pathways, which are related to cell growth, survival, and metabolism, suggesting that DOM300 might induce neurotoxicity in E. fetida. Altogether, these results may contribute to a better understanding of the toxicity and defense mechanisms of biochar-derived DOM on earthworms, especially during long-term applications, and thus provide guidelines for using biochar as a soil amendment.

Role of biochar-derived DOM compositions in enhanced biodegradation of sulfamethoxazole and chloramphenicol

In the study, we investigated the different compositions of biochar-derived dissolved organic matter (BDOM) that play a key role in the biodegradation of sulfamethoxazole (SMX) and chloramphenicol (CAP) by P. stutzeri and S. putrefaciens, and found that aliphatic compounds in Group 4, fulvic acid like in Region III, and solid microbial byproduct like in region IV are key common factors. The growth and antibiotic degradation efficiency of P. stutzeri and S. putrefaciens are positively correlated with the content of Group 4 and Region III, and negatively correlated with Region IV. This is consistent with the optimal biodegradation results of BDOM700 with the highest content of Group 4 and Region III. Additionally, the degradation efficiency of SMX by Pseudomonas stutzeri is negatively correlated with the percentage of polycyclic aromatics in Group 1, but not with CAP. Similarly, the percentage of fatty acids in S. putrefaciens was positively correlated with Group 1, whereas P. stutzeri did not. This indicates that some components of BDOM have varying effects on different bacteria or types of antibiotics. This study provides new insights into enhancing antibiotic biodegradation by controlling the composition of BDOM.

Characteristics of dissolved organic matter composition in biochar: Effects of feedstocks and pyrolysis temperatures.

Biochar has widely used in soil pollution remediation due to its advantages of high efficiency and environmental sustainability. Dissolved organic matter (DOM) released by biochar plays a non-negligible role in the migration and transformation of pollutants in environment, and its composition was regarded as main impact factor. In this study, 28 biochar were investigated to detect the effect of pyrolysis temperature and feedstock on DOM content and components. Results showed that the content of DOM released from biochar at low pyrolysis temperatures (300-400 ℃) was higher than that from high pyrolysis temperatures (500-600 ℃). In addition, the specific UV-Visible absorbance at 254nm (SUVA254) results expressed that DOM from peanut shell biochar (PSBC), rice husk biochar (RHBC) and bamboo biochar (BBC) had higher humification at high temperatures. Moreover, one fulvic acid-like (C2) and two humic acid-like (C1, C3) substances were main fluorescent components of biochar-derived DOM identified by parallel factor analysis based on excitation emission matrices fluorescence spectroscopies (EEM-PARAFAC). With the increase of pyrolysis temperature, humic acid substances content gradually decreased. The correlation analysis results revealed that pyrolysis temperatures and O/C, H/C, DOM content, the biological index (BIX), humification index (HIX), C1% and C3% was negatively correlated (p < 0.001). Thus, the pyrolysis temperatures take important roles in composition of DOM released from biochar, and this research would provide a reference for the application of biochar in the environment.

Effect of endogenetic dissolved organic matter on tetracycline adsorption by biochar.

The endogenetic biochar-derived dissolved organic matter (BDOM) might interact with pollutants in the environment. In this study, tetracycline (TC) was selected as the representative pollutant, and corn straw biochar (pyrolyzed at 300 °C) was used as the adsorbent. Through batch experiments and microscopic characterization, the releasing kinetics of BDOM and its effect on TC adsorption on biochar were investigated. The results showed that BDOM with weaker aromaticity and higher molecular weight was preferentially released. BDOM release led to the decrease of specific surface area (from 4.02 to 1.83 m2/g), mesopore number, and aromaticity of biochar (H/C increased from 0.80 to 0.91) and consequently weakened the pore filling of TC on biochar, hydrophobic interaction, and π-π EDA (electron donor receptor) interaction between biochar and TC. In addition, the released BDOM could form a complex with TC in solution to prevent TC adsorption on biochar. Overall, the change in the structural properties of biochar caused by BDOM release had a greater impact on the inhibition of TC adsorption than that of BDOM and TC complexation in this study. Through EEM-PRARFAC, BDOM contained about 63% humic acid-like fluorescent component and 37% tryptophan-like fluorescent component; the former (logKb values were 7.31 and 6.48, respectively) had a stronger binding strength with TC than the latter (logKb was 6.45). The findings of this study could provide some useful evidence for the removal of organic pollutants in soil and water environments and biochar application in pollution remediation.

Characterization of dissolved organic matter in biochar derived from various macroalgae (Phaeophyta, Rhodophyta, and Chlorophyta): Effects of pyrolysis temperature and extraction solution pH

Characterization of biochar-derived dissolved organic matter (DOM) can provide deep insight into potential applications of biochar. Herein, biochar from six macroalgae (Phaeophyta—Sargassum fusiforme, Sargassum thunbergii, and Sargassum vachellianum; Rhodophyta—Grateloupia turuturu and Chondria crassicaulis; and Chlorophyta—Ulva pertusa) were subjected to pyrolysis at different temperatures (200 °C–500 °C). The effects of pyrolysis temperature and extraction solution pH on the characteristics of the macroalgal biochar-derived DOM (MBDOM) were investigated via fluorescence excitation–emission matrix spectroscopy with parallel factor (PARAFAC) analysis. Five humic-like substances and one protein-like substance were identified. The distributions of the six PARAFAC components depended on the macroalgae species, pyrolysis temperature, and extraction solution pH. The proportion of the protein-like substance (0 %–46.77 %) was less than that of the humic-like substances (100 %–53.23 %) in a given MBDOM regardless of the extraction solution pH values. Fluorescence spectral indicators show that DOM from macroalgal biochar is more autochthonous and humified than that from the corresponding biomass. Hierarchical cluster analysis and redundancy analysis results further show that the macroalgae species, pyrolysis temperature, and extraction solution pH jointly affect DOM characteristics with varying contribution levels.

The mechanism of p-nitrophenol degradation by dissolved organic matter derived from biochar

Recently, p-nitrophenol (PNP), a common organic environmental pollutant, has been reported to be degraded by biochar. Although the degradation mechanism of PNP by biochar has been explored, the role of biochar-derived dissolved organic matter (BDOM) in PNP degradation remains unclear. Two BDOM samples were prepared in this study, and their PNP degradation performance was analyzed. BDOM5 (prepared at 500 °C) exhibited higher PNP degradation ratio than BDOM7 (prepared at 700 °C). The extent of PNP degradation per unit of BDOM5 and BDOM7 reached 9.54 and 4.19 mg/mg, respectively. Gas chromatography–mass spectrometry (GC–MS) analysis showed that both oxidative and reductive processes contributed to the PNP degradation by BDOM. Compared with BDOM7, the higher PNP removal of BDOM5 was due to the higher electron exchange capacity. Furthermore, hydroxyl radicals (OH) played a critical role in the oxidative degradation process of PNP by BDOM. This study sheds light on the phenomenon of PNP degradation by BDOM and these results may be useful for accurately assessing the environmental impact of biochar application.

Characterization of copper binding to biochar-derived dissolved organic matter: Effects of pyrolysis temperature and natural wetland plants.

Characterization of the biochar-derived dissolved organic matter (BDOM) is essential to understanding the environmental efficacy of biochar and the behavior of heavy metals. In this study, the binding properties of BDOM derived from different pyrolysis temperatures, wetland plants, and plant organs with Cu was investigated based on a multi-analytical approach. In general, the pyrolysis temperature exhibited a more significant impact on both the spectral characteristics of BDOM and Cu binding behavior than those of the feedstocks. With the pyrolysis temperature increased, the dissolved organic carbon, aromaticity, and fluorescence substance of BDOM decreased and the structure became more condensed. Humic-and tryptophan-like substance was more susceptible to the addition of Cu for BDOM pyrolyzed at 300℃ and 500℃, respectively. In addition, the more tyrosine-like substance is involved in Cu binding at higher pyrolysis temperature (500℃). However, the fluvic-like substance occurred preferentially with Cu than the other fluorophores. Moreover, the higher binding capacity for Cu was exhibited by the humic-like substance and by BDOM derived from the higher pyrolysis temperature and the lower elevation plants with the corresponding average stability constants (log KM) of 5.58, 5.36, and 5.16.

Insight into disinfection byproduct formation potential of aged biochar and its effects during chlorination.

Biochar can achieve multiple benefits including solid waste management, polluted water remediation, carbon sequestration, and emission reduction. However, various environmental factors (such as temperature variations and dry-wet alternation) and microbial activity may lead to the fragmentation, dissolution, and oxidation of biochar. These accelerate the dissolution of biochar-derived dissolved organic matter (DOM) and then influence disinfection byproducts formation potential (DBPFP) throughout the water treatment process. In this paper, biochars from six biomass feedstocks with five aging processes were prepared, and the DBPFP of biochar and its derived DOM were first studied systematically. Different aging processes might increase the DBPFP of biochar by increasing DOM content and changing the fraction distribution of DOM derived from biochar. Especially, the DBPFP of biochar increased apparently with the chemical aging process. Coexisting with the environmental concentration of humic acid, even aged biochar showed the potential to reduce DBPFP and integrated toxic risk value of the mixed system. In this study, the DBPFP of biochar-derived DOM during the disinfection process is confirmed, and the results can give information to the selection of biomass feedstocks of biochar and its service life in the water treatment process.

Assessment of potential biotoxicity induced by biochar-derived dissolved organic matters to biological fermentative H2 production

Biochar is a widely used antecedent for improving bio‑hydrogen production. However, little is known about the impact of biochar-derived dissolved organic matter (DOM) on the performance of fermentative bio-H2 production. Herein, we evaluated the impact of biochar-derived DOM on the fermentation performance of hydrogen-producing microflora. The pyrolysis temperature of biochar affected the DOM composition, with lower pyrolysis temperatures showing more serious inhibition on H2 accumulation. When biochar was pyrolyzed at 500 °C, DOM prolonged the fermentation period and decreased H2 production from 1330.41 mL L−1 to 1177.05 mL L−1 compared to the control group. The xylose utilization in mixed substrate decreased from 29.72% to 26.41%, which is not favorable for practical applications where lignocellulosic biomass is used as a substrate. Otherwise, DOM caused a 6% reduction in microbial biomass accumulation and less soluble metabolites formation. The potential mechanism of DOM inhibiting bio‑hydrogen production was verified by identifying an increase in reactive oxygen species (ROS) level (178.2%) and the microbial community shifted to containing fewer hydrogen-producing strains. The finding prompts a more precise design of biochar applications in fermentation systems to alleviate the potential hazards and maximum the fermentation performance, not limited to fermentative hydrogen production system.

Contribution of different mechanisms to Pb2+ and Cd2+ sorption on magnetic wheat straw biochars: Impact of pyrolysis temperature and DOM in biochar

This work quantitatively studied the sorption of Pb2+ and Cd2+ on magnetic biochars (MBCs) pyrolyzed at temperatures of 300, 500 and 700 °C and the effect of biochar-derived dissolved organic matter (BDOM) on Pb2+ and Cd2+ sorption. Surface characteristics of the MBCs before and after sorption were analyzed using Boehm titration and various spectroscopic techniques. For Pb2+, with increasing pyrolysis temperature, the sorption amounts by precipitation and coordination with π electrons increased from 63.5 to 109.3 mg/g and from 27.0 to 84.9 mg/g, respectively. While the sorption amount by complexation decreased from 34.5 to 16.5 mg/g. The contribution of precipitation (45.9–52.5%) and coordination with π electrons (19.5–39.1%) increased with increasing pyrolysis temperature, while contribution of complexation (7.6–24.9%) decreased. Increased ash content and aromaticity with pyrolysis temperature played the key roles in the change of Pb2+ sorption. The ion exchange and precipitation mechanisms dominated Cd2+ sorption on MBCs. Their respective sorption amounts were in the ranges of 5.08–10.36 and 1.31–9.82 mg/g, accounting for 48.8–72.5% and 18.7–46.3% of the total sorption, respectively. The change of ion-exchangeable sites on minerals with pyrolysis temperature is the main reason influencing the sorption via ion exchange for Cd2+. Unlike MBC500 and MBC700, removing BDOM from pristine biochar of MBC300 enhanced the total amounts of Pb2+ and Cd2+ sorption by 1.2 and 3.6 times, respectively, which was attributed to the enhanced sorption via ion exchange, precipitation and complexation for Pb2+ and enhanced sorption via ion exchange and precipitation for Cd2+. Therefore, the DOM-removed low-temperature MBC is a promising sorbent for treating heavy metal polluted waters.

Qualitative and quantitative investigation on adsorption mechanisms of Cd(II) on modified biochar derived from co-pyrolysis of straw and sodium phytate

Developing effective modification methods and obtaining a comprehensive understanding of adsorption mechanisms are essential for the practical application of biochars for the removal of heavy metals from solutions. In this study, rice straw was impregnated with sodium phytate and pyrolyzed at 350 °C, 450 °C, and 550 °C to synthesize modified biochars (i.e., MBC350, MBC450, and MBC550). The Cd(II) adsorption capacities and contributions of different mechanisms, including the effects of biochar-derived dissolved organic matter (BDOM), were investigated using batch sorption experiments and characterization analyses. The modification of sodium phytate promoted the pyrolysis of biomass, thereby increasing the BDOM content and aromatic structures at low and high pyrolysis temperatures, respectively. Moreover, the modification also increased the exchangeable Na+ and carbonate contents in the modified biochars. Compared with the raw biochars, the Cd(II) adsorption capacities of modified biochars increased by 3.3–4.3 times, and MBC550 had the highest Cd(II) adsorption capacity (126.5 mg/g), of which precipitation with minerals and interaction with π-electrons contributed 41.7% and 45.8%, respectively. However, at a lower pyrolysis temperature, the Cd(II) adsorption attributed to ion exchange and co-deposition with BDOM significantly increased, especially on MBC350 (33.9 and 12.6 mg/g, respectively). These results indicate that modification by sodium phytate effectively enhanced various adsorption mechanisms, thereby increasing the Cd(II) adsorption capacity. In addition, the contribution of co-deposition with BDOM to adsorption was unneglectable for the biochars pyrolyzed at low temperatures.