The behavior and composition of hydrochar-based dissolved organic matter (DOM) would affect the efficiency of copper (Cu) removal from wastewater through adsorption. In this study, the reed was ...hydrolyzed in the presence of feedwater with and without ZnCl2, FeCl3, and SnCl4 to produce pristine hydrochars (PHCs), which were named H2O-HC, ZnCl2-HC, FeCl3-HC, and SnCl4-HC. After removal of DOM, washed hydrochars (WHCs) were obtained, labelled as W–H2O-HC, W-ZnCl2-HC, W-FeCl3-HC, and W-SnCl4-HC. The release dynamics of DOM from PHCs were analyzed, and the adsorption behaviors of Cu2+ on both PHCs and WHCs were investigated. The results showed that chloride-modifications were beneficial for the porosity, specific surface area (SSA), and functional groups of WHCs. Meanwhile, the quantity of hydrochar-based DOM was significantly affected by chloride-modifications. In particular, the relative contents of Ar–P and Fa-L in the DOM released from hydrochars varied with time and modification. Furthermore, the Qe of Cu2+ adsorption on WHCs followed the order of W-SnCl4-HC > W-FeCl3-HC > W-ZnCl2-HC > W–H2O-HC at 15 °C. Compared to PHCs, the adsorption capacity of Cu2+ on WHCs was improved by 7.15–119.77% at the temperature of 35 °C. Simultaneously, the adsorption capacity of Cu2+ in WHCs showed a significant correlation with the SSA via physical adsorption (P < 0.05). Moreover, XPS analysis revealed that Cu2+ adsorption also occurred via complexation and chelation through newly formed Cu–O group between W-SnCl4-HC and Cu2+. Notably, the increase of Cu2+ adsorption in WHCs was significantly correlated with the release of Fa-L and Ar–P from PHCs (P < 0.05). This study found that the content and composition of hydrochar-based DOM could be a major driving factor for Cu2+ adsorption.
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•The adsorption performance of chlorides-modified hydrochars for Cu2+ was studied.•The Qe of Cu2+ adsorption followed the order of W-SnCl4-HC > W-FeCl3-HC > W-ZnCl2-HC > W–H2O-HC at 15 °C.•Cu2+ removal efficiency of hydrochars was improved significantly by removing DOM.•Due to complexation, DOM should not be overlooked in the adsorption of Cu2+ on hydrochars.
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•Lignin content is inversely proportional to DOM release from the biochar.•Biochar pyrolyzed sawdust with more lignin extracted less Fe from soil.•Sawdust biochar with less lignin can ...enhance the As leaching from soil.
Biochar is widely used material whose physical and chemical characteristics been widely investigated. Nevertheless, dissolved organic matter (DOM) released from biochar has received relatively little attention. In particular, little research has been conducted to understand the effects of feedstock biomass components on biochar DOM release. To control the amount of DOM released from biochar, this study focuses on the role of lignin, a component of biomass. To this end, samples of sawdust containing different lignin contents and a binary mixture of cellulose and lignin were pyrolyzed at 400 and 700 °C, and then the physico-chemical properties of the resulting biochar, and Fe(II) and As mobility were investigated in arsenic-contaminated soil amended by the biochar. This study showed that lignin is an critical factor in controlling the release of DOM. The amount of DOM released from the sawdust biochar with the lowest lignin content was 33% (400 °C) and 44% (700 °C) lower than those produced from lignin-rich biochar (sawdust without the extraction of lignin). The amount of oxalic acid in DOM decreased with increased lignin content. In addition, As mobility and the transformation of Fe(II) were minimized when lignin-rich biochar was applied to the As-contaminated soil. More importantly, these results suggest that controlling the lignin content of biomass can be universally applied to predict DOM concentrations of the biochars produced.
Persulfate advanced oxidation technology is widely utilized for remediating organic-contaminated groundwater. Post-remediation by persulfate oxidation, the aromaticity of dissolved organic matter ...(DOM) in groundwater is significantly reduced. Nevertheless, the evolution trends of aromaticity and related structural changes in DOM remained unclear. Here, we selected eight types of DOM to analyze the variation in aromaticity, molecular weight, and fluorescence characteristics during oxidation by persulfate using optical spectroscopy and parallel faction analysis combined with two-dimensional correlation spectroscopy analysis (2D PARAFAC COS). The results showed diverse trends in the changes of aromaticity and maximum fluorescence intensity (Fmax) among different types of DOM as the reaction time increases. Four types of DOM (humic acid 1S104H, fulvic acid, and natural organic matters) exhibited an initially noteworthy increase in aromaticity followed by a decrease, while others demonstrated a continuous decreasing trend (14.3%–69.4%). The overall decreasing magnitude of DOM aromaticity follows the order of natural organic matters ≈ commercial humic acid > fulvic acid > extracted humic acid. The Fmax of humic acid increased, exception of commercial humic acid. The Fmax of fulvic acid initially decreased and then increased, while that of natural organic matters exhibited a decreasing trend (86.4%). The fulvic acid-like substance is the main controlling factor for the aromaticity and molecular weight of DOM during persulfate oxidation process. The oxidation sequence of fluorophores in DOM is as follows: fulvic-like substance, microbial-derived humic-like substance, humic-like substance, and aquatic humic-like substance. The fulvic-like and microbial-derived humic-like substances at longer excitation wavelengths were more sensitive to the response of persulfate oxidation than that of shorter excitation wavelengths. This result reveals the structure evolution of DOM during persulfate oxidation process and provides further support for predicting its environmental behavior.
•Aromaticity in eight DOM decreased by 14.3%–69.4% after 32 h of oxidation•Persulfate system enhanced fluorescence intensity of HA extracted from environment•Fulvic acid-like substance reflected the aromaticity and molecular weight in DOM•The evolution mechanism of fluorophores was elucidated by 2D PARAFAC COS
•Microbes promoted the dissolution of oxides on mineral surfaces in water.•Extracellular polymeric substances contributed to mineral biotransformation.•Electronic transfer between minerals and ...microbes changed the mineral activation.•FT-ICR-MS measured the decomposition of organic matters at the molecular level.•Biotransformation of minerals inhibited the decomposition of organic matters.
Photochemical reactions that widely occur in aquatic environments play important roles in carbon fate (e.g., carbon conversion and storage from organic matter) in ecosystems. Aquatic microbes and natural minerals further regulate carbon fate, but the processes and mechanisms remain largely unknown. Herein, the interaction between Escherichia coli and pyrite and its influence on the fate of carbon in water were investigated at the microscopic scale and molecular level. The results showed that saccharides and phenolic compounds in microbial extracellular polymeric substances helped remove pyrite surface oxides via electron transfer. After the removal of surface oxides on pyrite, the photochemical properties under visible-light irradiation were significantly decreased, such as reactive oxygen species and electron transfer capacity. Unlike the well-accepted theory of minerals protecting organic matter in the soil, the organic matter adsorbed on minerals preferred degradation due to the enhanced photochemical reactions in water. In contrast, the minerals transformed by microbes suppressed the decomposition of organic matter due to the passivation of the chemical structure and activity. These results highlight the significance of mineral chemical activity on organic matter regulated by microbes and provide insights into organic matter conversion in water.
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Dissolved organic matter (DOM), as the most active ingredient in compost, directly determines the speciation and environmental behavior of HMs. Here, the binding properties of DOM derived from ...chicken-manure compost (CHM), cow-manure compost (COM) and pig-manure compost (PIM) with HMs were explored by analyses of Fluorescence excitation-emission matrix parallel factor (EEM-PARAFAC) and two-dimensional correlation Fourier transform infrared spectroscopy (2D-FTIR-COS). Results showed that the binding characteristics vary with origin of DOM and type of HMs. The fulvic-like component dominated the transformation of HMs speciation, and CHM-DOM had higher affinity with HMs and greater risk causing pollution due to its higher aromaticity, molecular weight and distribution of fluorescent components. Moreover, Cu(II) can efficiently bind to DOM with the stability constants (log kM) ranging from 4.53 to 5.38, followed by Pb(II) (3.34–3.57), whereas Cd(II) can hardly bind to DOM. The amide and polysaccharide were the predominant sites for HMs binding in CHM-DOM, and polysaccharide and phenolic in COM-DOM, while phenolic and amide in PIM-DOM, respectively. Although the proportion of protein-like components and non-fluorescent polysaccharides in DOM were low, their role in HMs binding should not be ignored. In brief, the environmental risk caused by livestock manure compost may originate from interactions between DOM and HMs.
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•Binding characteristics vary with origin of DOM and type of HMs.•CHM-DOM may cause environmental risk due to its interaction with HMs.•Protein and polysaccharides should not be ignored in HMs binding.
Sponge holobionts (i.e., the host and its associated microbiota) play a key role in the cycling of dissolved organic matter (DOM) in marine ecosystems. On coral reefs, an ecological shift from ...coral-dominated to algal-dominated ecosystems is currently occurring. Given that benthic corals and macroalgae release different types of DOM, in different abundances and with different bioavailability to sponge holobionts, it is important to understand how the metabolic activity of the host and associated microbiota change in response to the exposure to both DOM sources. Here, we look at the differential gene expression of two sponge holobionts 6 hours after feeding on naturally sourced coral- and macroalgal-DOM using RNA sequencing and meta-transcriptomic analysis. We found a slight, but significant differential gene expression in the comparison between the coral- and macroalgal-DOM treatments in both the high microbial abundance sponge Plakortis angulospiculatus and the low microbial abundance sponge Haliclona vansoesti. In the hosts, processes that regulate immune response, signal transduction, and metabolic pathways related to cell proliferation were elicited. In the associated microbiota carbohydrate metabolism was upregulated in both treatments, but coral-DOM induced further lipid and amino acids biosynthesis, while macroalgal-DOM caused a stress response. These differences could be driven by the presence of distinct organic macronutrients in the two DOM sources and of small pathogens or bacterial virulence factors in the macroalgal-DOM. This work provides two new sponge meta-transcriptomes and a database of putative genes and genetic pathways that are involved in the differential processing of coral- versus macroalgal-DOM as food source to sponges with high and low abundances of associated microbes. These pathways include carbohydrate metabolism, signaling pathways, and immune responses. However, the differences in the meta-transcriptomic responses of the sponge holobionts after 6 hours of feeding on the two DOM sources were small. Longer-term responses to both DOM sources should be assessed to evaluate how the metabolism and the ecological function of sponges will be affected when reefs shift from coral towards algal dominance.
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•Interaction between BSA and four antibiotics was studied by fluorescence quenching.•Static quenching occurred and binding ability followed order: TTC > CPC > OTC > PEG.•β-lactam ...showed higher removal rate than tetracycline by γ-radiation only or with BSA.•No correlation between k/kBSA and the binding affinity was observed.•BSA has little effect trend of abatement of antimicrobial activity by γ-irradiation.
In this study, to explore the influence of protein on antibiotics degradation during ionizing irradiation, the binding interaction between bovine serum albumin (BSA) and the broad spectrum β-lactam and tetractycline antibiotics and its effect on antibiotic degradation were investigated. Static quenching happened between BSA and antibiotics involving penicillin G (PEG), cephalosporin C (CPC), oxytetracycline (OTC) and tetracycline hydrochloride (TTC), indicating the formation of non-fluorescence complexes. The binding capacity followed the order: TTC > CPC > OTC > PEG. As exposed to γ-irradiation, the β-lactam antibiotics showed a higher degradation rate than the tetracyclines. The degradation rate constant (k) of CPC and PEG was 1.4–2.0 times higher than that of OTC and TTC. In presence of BSA, the k values (kBSA) of all the four antibiotics decreased greatly and the degradation rate of CPC and PEG was still higher by 1.2–1.3 times than that of OTC and TTC. No correlation between k/kBSA and the binding affinity was observed. The presence of BSA has little effect on the trend of abatement of antimicrobial activity to S. aureus during γ-irradiation. This suggests that the inhibition of protein to antibiotic degradation was mainly attributed to the competition of protein for the active species such as ·OH radical formed during γ-irradiation, while the binding ability of protein to antibiotics has no obvious effect. The results of this study contributed to develop technical strategies to improve the removal of antibiotics completely in real water matrices.
In recent years, rigid analogs of phenylalkylamine hallucinogens have appeared as recreational drugs. Examples include 2-(8-bromo-2,3,6,7-tetrahydrobenzo1,2-b:4,5-b′difuran-4-yl)ethan-1-amine ...(2C-B-FLY) and 1-(8-bromobenzo1,2-b;4,5-b’difuran-4-yl)-2-aminopropane (Bromo-DragonFLY, DOB-DFLY). Although some rigid compounds such as DOB-DFLY reportedly have higher potency than their non-rigid counterparts, it is not clear whether the same is true for 2C-B-FLY and other tetrahydrobenzodifurans. In the present study, the head twitch response (HTR), a 5-HT2A receptor-mediated behavior induced by serotonergic hallucinogens, was used to assess the effects of 2,5-dimethoxy-4-bromoamphetamine (DOB) and its α-desmethyl homologue 2,5-dimethoxy-4-bromophenethylamine (2C-B), as well as their benzodifuranyl and tetrahydrobenzodifuranyl analogs, in C57BL/6J mice. DOB (ED50 = 0.75 μmol/kg) and 2C-B (ED50 = 2.43 μmol/kg) induced the HTR. The benzodifurans DOB-DFLY (ED50 = 0.20 μmol/kg) and 2C-B-DFLY (ED50 = 1.07 μmol/kg) had significantly higher potency than DOB and 2C-B, respectively. The tetrahydrobenzodifurans DOB-FLY (ED50 = 0.67 μmol/kg) and 2C-B-FLY (ED50 = 1.79 μmol/kg), by contrast, were approximately equipotent with their non-rigid counterparts. Three novel tetrahydrobenzodifurans (2C-I-FLY, 2C-E-FLY and 2C-EF-FLY) were also active in the HTR assay but had relatively low potency. In summary, the in vivo potency of 2,5-dimethoxyphenylalkylamines is enhanced when the 2- and 5-methoxy groups are incorporated into aromatic furan rings, whereas potency is not altered if the methoxy groups are incorporated into dihydrofuran rings. The potency relationships for these compounds in mice closely parallel the human hallucinogenic data. The high potency of DOB-DFLY is probably linked to the presence of two structural features (a benzodifuran nucleus and an α-methyl group) known to enhance the potency of phenylalkylamine hallucinogens.
•The hallucinogens 2C-B and DOB induced head twitches in mice.•Tethering the methoxy groups into a benzodifuran nucleus increased potency.•Tethering the methoxy groups into a tetrahydrobenzodifuran nucleus did not alter potency.•The benzodifuran hallucinogen Bromo-DragonFLY was highly potent in mice.
Dissolved organic matter (DOM) plays an important role in the biogeochemical function development of bauxite residue. Nevertheless, the DOM composition at the molecular level and its interaction with ...microbial community during soil formation of bauxite residue driven by eco-engineering strategies are still relatively unknown. In the present study, the DOM composition at the molecular level and its interactions with the microbial community in amended and revegetated bauxite residue were explored. The results showed that the amendment applications and revegetation enhanced the accumulation of unsaturated molecules with high values of double bond equivalent (DBE) and nominal oxidation of carbon (NOSC) and aromatic compounds with high values of modified aromaticity index (AImod) as well as the reduction of average weighted molecular mass of DOM molecules. Significant correlations between DOM molecules and the microbial community and Fe/Al oxides were found. DOM molecules were decomposed by the microbial community and sequestered onto Fe/Al oxides, which were the main driving factors that changed DOM chemodiversity in the amended and revegetated bauxite residue. These findings are beneficial for understanding the biogeochemical behaviours of DOM and providing a critical basis for the development of eco-engineering strategies towards soil formation and the sustainable revegetation of bauxite residue.
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•DOM molecules interaction with microbial community in revegetated bauxite residue were investigated.•Revegetation enhanced the enrichment of DOM and development of microbial community in bauxite residue.•Saturated DOM compounds transformed into unsaturated DOM compounds in revegetated bauxite residue.•Microbial community and Fe/Al oxides were the main driving factors influencing DOM chemodiversity.
The accessibility of iron (Fe) species for microbial processes is dependent on solubility and redox state, which are influenced by complexation with dissolved organic matter (DOM) and ...water-extractable organic matter (WEOM). We evaluated the complexation of these pools of organic matter to soluble Fe(II) and Fe(III) in the slightly acidic Schlöppnerbrunnen fen and subsequent effects on Fe(II) oxidation and Fe(III) reduction. We found the majority of soluble Fe(II) and Fe(III) is complexed to DOM. High-resolution mass spectrometry identified potential complexing partners in peat-derived water extracts (PWE), including compound classes known to function as ligands or electron shuttles, like tannins and sulfur-containing compounds. Furthermore, we observed clear differences in the stability of Fe(II)- and Fe(III)-DOM, with more labile complexes dominating the upper, oxic layers (0–10 cm) and more stable complexes in lower, anoxic layers (15–30 cm). Metal isotope-coded profiling identified a single potential chemical formula (C42H57O13N9Fe2) associated with a stable Fe-DOM complex. Fe(III) reduction and Fe(II) oxidation incubations with Geobacter sulfurreducens PCA and Shewanella oneidensis MR-1 or Sideroxydans CL-21, respectively, were used to determine the influence of Fe-DOM complexes on Fe cycling rates. The addition of PWE led to a 2.3-fold increase in Fe(III) reduction rates and 0.5-fold increase in Fe(II) oxidation rates, indicating Fe-DOM complexes greatly influence microbial Fe cycling by potentially serving as electron shuttles. Molecular analyses revealed Fe(III)-reducing and Fe(II)-oxidizing bacteria co-exist across all depths, in approximately equal proportions (representing 0.1–1.0% of the total microbial community), despite observed changes in redox potential. The activity of Fe(III)-reducing bacteria might explain the presence of the detected Fe(II) stabilized via complexation with DOM even under oxic conditions in upper peat layers. Therefore, these Fe(II)-DOM complexes can be recycled by microaerophilic Fe(II)-oxidizers. Taken together, these results suggest Fe-DOM complexation in the fen accelerates microbial-mediated redox processes across the entire redox continuum.
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•This field study of an Fe-rich peatland underlies the importance of Fe species determination.•The majority of Fe is complexed by DOM and keeps Fe(II) and Fe(III) in solution.•DOM stabilizes Fe(II) in oxic soil layers and contributes to the redox equilibria.•Fe-DOM-complexes enhance microbially-mediated Fe cycling.•Fe(II) and Fe(III) across all depths allows co-existence of Fe-cycling microorganisms.
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