Genome-Centric Metatranscriptomic Characterization of a Humin-Facilitated Anaerobic Tetrabromobisphenol A-Dehalogenating Consortium.

Tetrabromobisphenol A (TBBPA), a widely used brominated flame retardant in electronics manufacturing, has caused global contamination due to improper e-waste disposal. Its persistence, bioaccumulation, and potential carcinogenicity drive studies of its transformation and underlying (a)biotic interactions. This study achieved an anaerobic enrichment culture capable of reductively dehalogenating TBBPA to the more bioavailable bisphenol A. 16S rRNA gene amplicon sequencing and quantitative PCR confirmed that successive dehalogenation of four bromide ions from TBBPA was coupled with the growth of both Dehalobacter sp. and Dehalococcoides sp. with growth yields of 5.0 ± 0.4 × 108 and 8.6 ± 4.6 × 108 cells per µmol Br- released (N = 3), respectively. TBBPA dehalogenation was facilitated by solid humin and reduced humin, which possessed the highest organic radical signal intensity and reducing groups -NH2, and maintained the highest dehalogenation rate and dehalogenator copies. Genome-centric metatranscriptomic analyses revealed upregulated putative TBBPA-dehalogenating rdhA (reductive dehalogenase) genes with humin amendment, cprA-like Dhb_rdhA1 gene in Dehalobacter species, and Dhc_rdhA1/Dhc_rdhA2 genes in Dehalococcoides species. The upregulated genes of lactate fermentation, de novo corrinoid biosynthesis, and extracellular electron transport in the humin amended treatment also stimulated TBBPA dehalogenation. This study provided a comprehensive understanding of humin-facilitated organohalide respiration.

Adsorption of oxytetracycline on subalpine meadow soil from Zoige Plateau, China: Effects of the coexisting Cu2.

Subalpine meadow soil with high moisture and humus content is a unique soil type in the Zoige Plateau. Oxytetracycline and copper are common soil contaminants which interact to form compound pollution. Oxytetracycline's adsorption on natural subalpine meadow soil and its components (humin and the soil without iron and manganese oxides) was studied in the laboratory with and without the presence of Cu2+. The effects of temperature, pH and Cu2+ concentration were documented in batch experiments, allowing deduction of the main sorption mechanisms. The adsorption process had two phases: one rapid, taking place in the first 6 h, and another slower, reaching equilibrium at around 36 h. The adsorption kinetics were pseudo-second-order, and the adsorption isotherm conformed to the Langmuir model at 25 °C. Higher concentrations oxytetracycline increased the adsorption, but higher temperature did not. The presence of Cu2+ had no effect on the equilibrium time, but the amount and rate adsorbed were much greater with Cu2+ concentration increased (except for the soil without iron and manganese oxides). The amounts adsorbed with/without Cu2+ were in the order the humin from subalpine meadow soil (7621 and 7186 µg/g) > the subalpine meadow soil (7298 and 6925 µg/g) > the soil without iron and manganese oxides (7092 and 6862 µg/g), but the difference among those adsorbents was slight. It indicates that humin is a particularly important adsorbent in the subalpine meadow soil. The amount of oxytetracycline adsorbed was greatest at pH 5-9. In addition, Surface complexation through metal bridging was the most important sorption mechanism. Cu2+ and oxytetracycline formed positively-charged complex that was adsorbed and then formed a ternary complex "adsorbent-Cu(II)-oxytetracycline", in which Cu2+ acted as a bridge. These findings provide a good scientific basis for soil remediation, and for assessing environmental health risks.

Biogenic ferrihydrite-humin coprecipitate as an electron donor for the enhancement of microbial denitrification by Pseudomonas stutzeri.

Nitrate pollution of groundwater has become an increasingly serious environmental problem that poses a great threat to aquatic ecosystems and to human health. Previous studies have shown that solid-phase humin (HM) can act as an additional electron donor to support microbial denitrification in the bioremediation of nitrate-contaminated groundwater where electron donor is deficient. However, the electron-donating capacities of HMs vary widely. In this study, we introduced ferrihydrite and prepared ferrihydrite-humin (Fh-HM) coprecipitates via biotic means to strengthen their electron-donating capacities. The spectroscopic results showed that the crystal phase of Fh did not change after coprecipitation with HM in the presence of Shewanella oneidensis MR-1, and iron may have complexed with the organic groups of HM. The Fh-HM coprecipitate prepared with an optimal initial Fh-HM mass ratio of 14:1 enhanced the microbial denitrification of Pseudomonas stutzeri with an electron-donating capacity 2.4-fold higher than that of HM alone, and the enhancement was not caused by greater bacterial growth. The alginate bead embedding assay indicated that the oxidation pathway of Fh-HM coprecipitate was mainly through direct contact between P. stutzeri and the coprecipitate. Further analyses suggested that quinone and organic-complexed Fe were the main electron-donating fractions of the coprecipitate. The results of the column experiments demonstrated that the column filled with Fh-HM-coated quartz sand exhibited a higher denitrification rate than the one filled with quartz sand, indicating its potential for practical applications.

Humin-promoted microbial electrosynthesis of acetate from CO2 by Moorella thermoacetica.

Humin, an insoluble fraction of humic substances at any pH, has been reported to be an extracellular electron mediator (EEM) that functions in carbon dioxide (CO2 )-fixing acetogenesis. Here, we show that humin promotes the microbial electrosynthesis (MES) of acetate from CO2 using Moorella thermoacetica. Yeast extract, essential for the reaction of M. thermoacetica, resulted in the heterotrophic production of organic acids including acetate, hydrogen, and methane. Excluding the effect of yeast extract, MES with 13 g/L of suspended humin poised at -510 mV (vs. Ag/AgCl) achieved a CO2 -fixing acetate production of 24.2 mg-acetate/L/day (1.9 mg-acetate/day/g-humin); this is 10-folds higher than the humin-free MES, with 90.3% of the coulombic efficiency. Although M. thermoacetica is an electroactive bacterium, it obtains electrons for acetogenesis mostly via humin. The suspended humin-assisted MES poised at -810 mV (vs. Ag/AgCl) increased the acetate production rate to 39.3 mg-acetate/L/day using electrons mainly from electrolyzed hydrogen and humin. Immobilization increased the humin's EEM efficiency, as indicated by the acetate production rate of 20.8 mg-acetate/L/day (6.9 mg-acetate/day/g-humin) with a 98.7% coulombic efficiency in MES with 3 g/L of immobilized humin poised at -510 mV (vs. Ag/AgCl). These results suggest that humin-assisted MES has high potential for microbial CO2 fixation.

Redox reaction between solid-phase humins and Fe(III) compounds: Toward a further understanding of the redox properties of humin and its possible environmental effects.

Redox reactions between humic substances and Fe(III) compounds play a critical role in the biogeochemical cycle of pollutants. Most humic substances in soils and sediments are in a solid form (i.e. humin (HM)). In order to assess the contribution of electron shuttling via HM within the electron transfer network in natural environments and to predict environmental fate of pollutants associated with iron oxides, it is necessary to understand the electron transfer processes from HM to the environmentally relevant Fe(III) minerals, and to examine the redox reversibility of HM. The results of this study demonstrated that non-reduced HMs could only donate electrons to dissolved ferric citrate and poorly crystalline ferrihydrite, but reduced HMs could also reduce hematite and magnetite that had high crystallinity. The degree of reduction depended on the difference in redox potential and the crystallinity of the Fe(III) compounds. The electron-accepting capacities of different HMs correlated well with their organic carbon content, and quinones and Fe-bound organic component were important electron-accepting groups in HMs. Furthermore, the redox reversibility experiments demonstrated that HMs could maintain stable electron transfer capacities over three reduction-oxidation cycles, indicating that the HM could be an environmentally sustainable electron shuttle. Our results suggest that (1) HM may play an unrecognized and important role in biogeochemical cycles of pollutants in Fe(III) mineral-rich environments; (2) electron shuttling through HM to ferric citrate and ferrihydrite can occur even in the presence of O2; and (3) HM would be a promising material for environmental remediation.

Optimized isolation method of humin fraction from mineral soil material.

Humic substances, including humin fraction, play a key role in the fate of organic and inorganic xenobiotics contaminating the environment. Humin is an important fraction of humic substances, which has been the least studied to date. This is due to the difficulties connected with its isolation that pose a number of methodological problems. Methods of humin fraction isolation can be divided into following main groups: (1) digestion of mineral soil components with HF/HCl followed by alkali extraction of HA and FA; (2) alkali extraction of HA and FA followed by extraction of humin by different organic solvents; and (3) alkali extraction of HA and FA followed by HF/HCl digestion of mineral soil components. Nevertheless, each of these methods has different limitations. We described in detail a useful procedure of humin isolation, in which this fraction was not extracted, but isolated from the soil by removing its soluble organic and mineral components. A modified method of HA and FA extraction with 0.1 M NaOH, according to the International Humic Substances Society, was used in the first step. Then, the mineral components in the residue were digested with the 10% HF/HCl. Unlike the procedures oriented to increase the concentration of organic matter, samples were treated several times with the HF/HCl mixture until the mineral fraction was almost completely digested. The main assumption of the method modification was to obtain the highest yield with the lowest possible ash content, but without affecting humin chemical structure. The results showed that the proposed procedure is characterized by a high efficiency and recovery and, therefore, it can be used to isolate high amounts of humin from soil.

Application of humin-immobilized biocathode in a continuous-flow bioelectrochemical system for nitrate removal at low temperature.

Solid-phase humic substances (humin) can work as an additional electron donor to support the low temperature denitrification but the reducing capacity of its non-reduced form is limited. In this study, a continuous-flow denitrifying BES with a humin-immobilized biocathode (H-BioC) was established. Humin was expected to function as a redox mediator and be persistently reduced on the cathode to provide reducing power to a denitrifying biofilm. Results showed that the H-BioC maintained a stable denitrification capacity with low nitrite accumulation for more than 100 days at 5 °C, and the specific microbial denitrification rate and electron transfer rate were 3.97-fold and 1.75-fold higher than those of the unaltered cathode. The results of repeated cycles of humin reduction and oxidation experiments further suggested that the redox activity of humin was stable. Acidovorax was the most dominant genus in both H-BioC biofilm and unaltered cathodic biofilm, while Rhodocyclaceae (unclassified_f_) was more enriched in H-BioC biofilm. Further Phylogenetic Investigation of Communities by Reconstruction of Unobserved States (PICRUSt) analyses indicated that biofilm formation, electron transfer, and nitrate reduction functions were more abundant in H-BioC, suggesting a possible enhancement mechanism by humin. The results of this study raise the possibility that immobilization of solid-phase humin may be a useful strategy for electrostimulated heterotrophic denitrification in groundwater where the indigenous bacteria have poor electroactivity.

Enhanced low-temperature denitrification by microbial consortium using solid-phase humin.

Reducing the use of liquid organic carbon electron donors during biostimulation of heterotrophic denitrification is critical for sustainable groundwater remediation. Solid-phase humin isolated from natural sources can provide a cost-effective alternative to classical electron donors. In this study, the low-temperature denitrification capacity of an acetate-fed microbial community was enhanced using humin at 20 °C and 10 °C. These enhancements were not caused by faster acetate consumption and greater bacterial growth with the addition of humin. Estimation of the electron balance and first-order kinetics suggested that the enhancement in denitrification occurred mainly after acetate exhaustion. Humin may therefore have acted as an additional electron donor for the denitrifying microbial community, with the reduced quinone group in humin potentially responsible for electron donation. The addition of humin increased the richness and diversity of the denitrifying microbial community, in which Dechloromonas spp. played a critical role. Given the prevalence of humin and denitrifiers using humic substances, our results have important implications in the bioremediation of nitrate-contaminated groundwater using less liquid organic carbon electron donors.

Determination of Organic Compounds, Fulvic Acid, Humic Acid, and Humin in Peat and Sapropel Alkaline Extracts.

Black, brown, and light peat and sapropel were analyzed as natural sources of organic and humic substances. These specific substances are applicable in industry, agriculture, the environment, and biomedicine with well-known and novel approaches. Analysis of the organic compounds fulvic acid, humic acid, and humin in different peat and sapropel extracts from Lithuania was performed in this study. The dominant organic compound was bis(tert-butyldimethylsilyl) carbonate, which varied from 6.90% to 25.68% in peat extracts. The highest mass fraction of malonic acid amide was in the sapropel extract; it varied from 12.44% to 26.84%. Significant amounts of acetohydroxamic, lactic, and glycolic acid derivatives were identified in peat and sapropel extracts. Comparing the two extraction methods, it was concluded that active maceration was more efficient than ultrasound extraction in yielding higher amounts of organic compounds. The highest amounts of fulvic acid (1%) and humic acid and humin (15.3%) were determined in pure brown peat samples. This research on humic substances is useful to characterize the peat of different origins, to develop possible aspects of standardization, and to describe potential of the chemical constituents.

Accelerating effects of humin on sulfide-mediated azo dye reduction.

As an important fraction of humic substances, humin has been found capable of stimulating bioreduction reactions. However, whether humin could promote abiotic reduction and the effects of coexisting soluble humic substance and insoluble mineral remained unsolved. In this study, a humin sample was isolated from a paddy soil. Cyclic voltammetry, electron paramagnetic resonance, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analyses of the humin indicated the existence of redox-active quinone moieties and other oxygen-containing groups. The humin could be reduced by sulfide and its presence stimulated the abiotic reduction of acid red 27 (AR27) and four other azo dyes by sulfide. In the presence of 100-1000 mg/L intact humin, the sulfide-mediated AR27 reduction efficiency in 7 d was enhanced from 56.3% to 92.5%. The stimulating behavior of intact humin was observed for 100-300 mg/L AR27 and increased with the increase of sulfide concentration (1.2-3.0 mM). Much higher stimulating effects were found with the presence of humin pre-reduced by sulfide. Moreover, for sulfide-mediated AR27 reduction, the coexistence of humin (500 mg/L) and humic acid (10-30 mg/L) or Wyoming sodium-montmorillonite (SWy-2, 1-4 g/L) led to better promotion activities than the presence of single component. And synergistic promotion of sulfide-mediated AR27 reduction was observed with coexisting humin and SWy-2 due to enhanced Fe(II) production. These findings extended our understanding of the influence of humin on reductive transformation of pollutants in the environment.

Natural organic matter residue as a low cost adsorbent for aluminum.

The contamination of aquatic and terrestrial environments by potentially toxic metals is highlighted by the possible impacts that their high availability can have on the environment. Thus, the development of alternative absorbents that can be used in the remediation of contaminated areas is of great environmental interest. Humin, one of the fractions of natural organic matter, is a promising alternative in studies on the retention of different metals that are environmentally toxic. In this study, the influence of the organic and inorganic humin constituents that are involved in the retention of aluminum species was evaluated. After extraction and calcination to obtain the ashes (inorganic constituents), humin and ash samples were structurally characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. Interaction studies between aluminum-humin and ash-humin were performed in the pH range of 4.0-8.0 and with various contact times. The results of the characterization of humin and ash showed different functional groups present in the structures of these materials. Based on the results of the interaction between humin-aluminum and ash-aluminum, it can be inferred that both the organic and inorganic components of humin are efficient at absorbing aluminum. However, the adsorption isotherms showed that humin and the ashes have different adsorption behaviors. Humin is the only fraction of natural organic matter with a significant inorganic constituent content; it is the fraction least used by researchers in this field and is often discarded as waste. In light of this, the results obtained in this work highlight the importance of humin as a natural adsorbent material. Humin may be promising for the removal of aluminum species in contaminated environments due to the presence of organic and inorganic constituents.

Effect of organic carbon chemistry on sorption of atrazine and metsulfuron-methyl as determined by (13)C-NMR and IR spectroscopy.

Soil organic matter (SOM) content is the major soil component affecting pesticide sorption. However, recent studies have highlighted the fact that it is not the total carbon content of the organic matter, but its chemical structure which have a profound effect on the pesticide's sorption. In the present study, sorption of atrazine and metsulfuron-methyl herbicides was studied in four SOM fractions viz. commercial humic acid, commercial lignin, as well as humic acid and humin extracted from a compost. Sorption data was fitted to the Freundlich adsorption equation. In general, the Freundlich slope (1/n) values for both the herbicides were <1. Except for atrazine sorption on commercial humic acid, metsulfuron-methyl was more sorbed. Desorption results suggested that atrazine was more desorbed than metsulfuron-methyl. Lignin, which showed least sorption of both the herbicides, showed minimum desorption. Sorption of atrazine was best positively correlated with the alkyl carbon (adjusted R (2) = 0.748) and carbonyl carbon (adjusted R (2) = 0.498) but, their effect was statistically nonsignificant (P = 0.05). Metsulfuron-methyl sorption showed best positive correlation with carbonyl carbon (adjusted R (2) = 0.960; P = 0.05) content. Sorption of both the herbicides showed negative correlation with O/N-alkyl carbon. Correlation of herbicide's sorption with alkyl and carbonyl carbon content of SOM fractions suggested their contribution towards herbicide sorption. But, sorption of metsulfuron-methyl, relatively more polar than atrazine, was mainly governed by the polar groups in SOM. IR spectra showed that H-bonds and charge-transfer bonds between SOM fraction and herbicides probably operated as mechanisms of adsorption.

Experimental and molecular dynamic simulation study of perfluorooctane sulfonate adsorption on soil and sediment components.

Soil and sediment play a crucial role in the fate and transport of perfluorooctane sulfonate (PFOS) in the environment. However, the molecular mechanisms of major soil/sediment components on PFOS adsorption remain unclear. This study experimentally isolated three major components in soil/sediment: humin/kerogen, humic/fulvic acid (HA/FA), and inorganic component after removing organics, and explored their contributions to PFOS adsorption using batch adsorption experiments and molecular dynamic simulations. The results suggest that the humin/kerogen component dominated the PFOS adsorption due to its aliphatic features where hydrophobic effect and phase transfer are the primary adsorption mechanism. Compared with the humin/kerogen, the HA/FA component contributed less to the PFOS adsorption because of its hydrophilic and polar characteristics. The electrostatic repulsion between the polar groups of HA/FA and PFOS anions was attributable to the reduced PFOS adsorption. When the soil organic matter was extracted, the inorganic component also plays a non-negligible role because PFOS molecules might form surface complexes on SiO2 surface. The findings obtained in this study illustrate the contribution of organic matters in soils and sediments to PFOS adsorption and provided new perspective to understanding the adsorption process of PFOS on micro-interface in the environment.

Arsenite adsorption and oxidation affected by soil humin: The significant role of persistent free radicals and reactive oxygen species.

Humin (HM), as the main component of soil organic matter, carries various reactive groups and plays a crucial regulatory role in the transformation of arsenic (As). However, current research on the redox pathway of As and its interactions with HM is relatively limited. This study aimed to explore the impact of different HM samples on the redox characteristics of As. The results showed that HM can not only adsorb arsenite [As(III)] but also oxidize As(III) into arsenate [As(V)]. However, once As(III) is adsorbed on the HM, it cannot undergo further oxidation. HMNM (extracted from peat soil) exhibited the highest adsorption capacity of As(III), with a maximum amount of 1.95 mg/kg. The functional groups of HM involved in As complexation were primarily phenolic hydroxyl and carboxyl groups. The adsorption capacity of HM samples for As(III) was consistent with their carboxyl group contents. The oxygen-containing functional groups and environmentally persistent free radicals (EPFRs) on HM can directly oxidize As(Ⅲ) through electron transfer, or indirectly induce the production of reactive oxygen species (ROS), such as hydroxyl radicals, to further oxidize As(Ⅲ). This study provides new insight into the transport and transformation process of As mediated by soil HM, and establishes a theoretical basis for As remediation.

Formation/characterization of humin-mediated anaerobic granular sludge and enhanced methanogenic performance.

This study presents a novel method for accelerating the granulation of methanogenic anaerobic granular sludge (AnGS) in an upflow anaerobic sludge blanket (UASB) reactor using solid-phase humin (HM). The results demonstrated that HM-mediated AnGS (HM-AnGS) formed rapidly within 50 days. The increase in particle size, settling velocity and mechanical strength was attributed to the rapid granulation of the HM-AnGS. The maximum methane yield of the HM-AnGS was 5-fold higher than that of the control group. This is consistent with the findings, which showed that HM-AnGS had 3.2-3.4 times more methyl-coenzyme M reductase (Mcr) activity and 2.4-2.9 times more adenosine triphosphate (ATP) than control groups. Molecular analyses indicate that HM most likely accelerated interspecies electron transfer (IET) in HM-AnGS (e.g., from Enterococcus to Methanosaeta). Furthermore, the HM-AnGS was effective in recovering energy from actual slaughterhouse wastewater.

Effects of Aging on Adsorption of Tetracycline Hydrochloride by Humin.

To explore the effects of "aging", an environmental factor, on adsorption of tetracycline hydrochloride (TC) by humin (HM), this paper coats HM surface with ferric hydroxide precipitate to simulate the aging process. The research findings indicate that compared with fresh HM, aged HM (HM-Fe) displays an accelerated adsorption rate and higher adsorption capacity on TC. With an initial concentration of 20 mg·L-1, TC's equilibrium adsorption capacity on HM and HM-Fe is 4.6 and 5.3 mg·g-1, respectively, whereas the corresponding initial adsorption rate is 0.036 and 0.132 mg·g-1·min-1. The pseudo-second-order kinetic model and Freundlich adsorption isotherm model could adequately simulate the adsorption process of TC by HM and HM-Fe, suggesting the occurrence of chemical adsorption and multimolecular layer adsorption between TC and HM and HM-Fe. Based on ΔAbs deduced from Job's calculation, it can be assumed a complex reaction occurs between the iron element on the HM-Fe surface and TC, which acts as a sort of bridge in strengthening the adsorption of TC by HM-Fe. The aforesaid findings may provide subsequent further study on environmental behaviors of TC in the soil with both fundamental theories and a scientific basis.

Anaerobic mineralization of toluene by enriched soil-free consortia with solid-phase humin as a terminal electron acceptor.

The anaerobic biodegradation of toluene proceeds very slowly owing to limited electron acceptors in contaminated aquifer. The liquid reagents traditionally used to enhance this process readily migrate away from the contaminated site, and continuous addition would cause secondary pollution. In our previous study, the reduced solid-phase humic substances (humin), which are redox active, were found to act as electron donors to promote the microbial reactions. Here, we provide new evidence that humin can promote the anaerobic biodegradation of toluene as a terminal electron acceptor. When inoculating nitrate-reducing (NR) and iron-reducing (IR) consortia with toluene degradation activities, the average toluene degradation rates reached 21.20 ± 1.18 µmol/(L·d) and 15.43 ± 0.41 µmol/(L·d) in the presence of a sediment humin (HMcj), and 94.69% ± 4.26% and 93.20% ± 3.73% of the electrons released from toluene oxidation to CO2 could be recovered by the reduction of HMcj, respectively. Spectroscopy analyses revealed that quinone moieties and nitrogen-containing moieties may be the electron-accepting groups of HMcj. Based on 16S rRNA sequencing, Cellulomonas spp. were the possible functional bacteria in the culture with NR consortium as the inoculum, while Azospira spp., Cellulomonas spp. and Bacillus spp. were the possible functional bacteria in the culture with IR consortium as the inoculum. Further Phylogenetic Investigation of Communities by Reconstruction of Unobserved States (PICRUSt) analyses indicated that toluene oxidation and extracellular electron transfer functions were more abundant in HMcj amended cultures, suggesting a possible enhancement mechanism by HMcj. Additionally, experiments using natural groundwater illustrated that toluene degradation was highly dependent on its concentration, HMcj dosage, pH, and salinity. The study of a column filled with HMcj-coated quartz sand demonstrated a desirable level of toluene degradation in a continuous-flow mode without the presence of other electron acceptors. This study provided an effective and green approach for the remediation of the toluene-contaminated groundwater.

A new strategy for treating Pb2+ and Zn2+ pollution with industrial waste derivatives Humin.

Metal pollution caused by industrial waste accumulation is a long-term and far-reaching problem. Humin (HM), as a highly condensed organic component insoluble in alkaline or water solution, is often discarded as humic acid industrial waste. However, the abundant active functional groups in HM reported by some researches make it possible for HM to remove metals. In this study, a waste reuse strategy was proposed to reduce the pressure of industrial metal pollution on the environment. HM was obtained from lignite waste residue. Scanning electron microscopy, energy spectrum and Fourier infrared spectroscopy, combined with the adsorption models were employed to reveal the mechanism of HM adsorption. The results showed that HM had multiple adsorption mechanism and high biological stability. The adsorption capacity of HM to Zn2+ and Pb2+ were 194.88 mg/g and 289.59 mg/g respectively. HM adsorbed Zn2+ mainly by physical multilayer adsorption. And the adsorption of Pb2+ by HM was mainly a monolayer chemical reaction, which depended on its active functional groups and the exchange of valence electrons. Notably, HM could simultaneously remove Pb2+ and Zn2+ and almost did not affect its original adsorption capacity to single ions. These results will provide a new strategy for the treatment of metal pollution in the future and alleviate the pressure of multiple metal pollution of the environment.

Valorization of Glucose-Derived Humin as a Low-Cost, Green, Reusable Adsorbent for Dye Removal, and Modeling the Process.

Glucose can be isomerized into fructose and dehydrated into key platform biochemicals, following the "bio-refinery concept". However, this process generates black and intractable substances called humin, which possess a polymeric furanic-type structure. In this study, glucose-derived humin (GDH) was obtained by reacting D-glucose with an allylamine catalyst in a deep eutectic solvent medium, followed by a carbonization step. GDH was used as a low-cost, green, and reusable adsorbent for removing cationic methylene blue (MB) dye from water. The morphology of carbonized GDH differs from pristine GDH. The removal efficiencies of MB dye using pristine GDH and carbonized GDH were 52% and 97%, respectively. Temperature measurements indicated an exothermic process following pseudo-first-order kinetics, with adsorption behavior described by the Langmuir isotherm. The optimum parameters were predicted using the response surface methodology and found to be a reaction time of 600 min, an initial dye concentration of 50 ppm, and a GDH weight of 0.11 g with 98.7% desirability. The MB dye removal rate optimized through this model was 96.85%, which was in good agreement with the experimentally obtained value (92.49%). After 10 cycles, the MB removal rate remained above 80%, showcasing the potential for GDH reuse and cost-effective wastewater treatment.

Compositional changes in the humin fraction resulting from the long-term cultivation of an Irish grassland soil: Evidence from FTIR and multi-NMR spectroscopies.

Soil humin (HN), a major long-term sink for carbon in the pedosphere, plays a key role in the global carbon cycle, and has been less extensively studied than the humic and fulvic acids components. There are increasing concerns about the depletions of soil organic matter (SOM) arising from modern soil cultivation practices but there has been little focus on how HN can be altered as the result. This study has compared the HN components in a soil under cultivation for wheat for >30 years with those from an adjacent contiguous soil that had been under long-term grass for all that time. A urea-fortified basic solution isolated additional humic fractions from soils that had been exhaustively extracted in basic media. Then further exhaustive extractions of the residual soil material with dimethyl sulfoxide, amended with sulphuric acid isolated what may be called the "true" HN fraction. The long-term cultivation resulted in a loss of 53 % soil organic carbon in the surface soil. Infrared and multi-NMR spectroscopies showed the "true" HN to be dominated by aliphatic hydrocarbons and carboxylated structures, but with clear evidence for lesser amounts of carbohydrate and peptide materials, and with weaker evidence for lignin-derived substances. These lesser-amount structures can be sorbed on the soil mineral colloid surfaces and/or covered by the hydrophobic HN component or entrained within these which have strong affinities for the mineral colloids. HN from the cultivated site contained less carbohydrate and more carboxyl groups suggesting slow transformations took place resulting from the cultivation, but these were much slower than for the other components of SOM. It is recommended that a study be made of the HN in a soil under long-term cultivation for which the SOM content has reached a steady state and where HN will be expected to dominate the components of SOM.