Humic Research Articles

Enhanced gravity-driven membrane filtration for purifying roof rainwater using multi-walled carbon nanotubes tuned PVDF hollow fiber membranes

The collection and reuse of roof rainwater can alleviate water shortage for daily life. In this study, polyvinylidene fluoride hollow fiber membranes tuned with three multi-walled carbon nanotubes (pure MWCNTs, MWCNTs-COOH, and MWCNTs-OH) were prepared using a non-solvent induced phase separation method for gravity-driven membrane filtration to purify roof rainwater. The results showed that the MWCNTs were distributed on the membrane surface and throughout the porous structure of the cross-section, which changed the pore structure parameters and hydrophilicity. The pure water flux of the MWCNTs tuned membranes increased by 152.5 % at 1.0 bar, and the rejection rates of humic acid and bovine serum albumin increased from 97.4 % and 75.7 % to 98.9 % and 96.3 %, respectively. The extended Derjaguin, Landau, Verwey, and Overbeek (xDLVO) theory states that the presence of MWCNTs leads to changes in the physicochemical properties of the membrane surface, resulting in membranes with different anti-fouling behaviors. A gravity-driven membrane filtration test was continuously operated for 100 days, and all membranes removed 25.0–26.7 %, 49.5–53.0 %, and 89.0–93.3 % of total dissolved solids, dissolved organic carbon, and turbidity from roof rainwater, respectively. However, the pure MWCNTs modified membrane with relatively hydrophobic properties showed a 12.4 % increase in flux over the unmodified membrane. Importantly, the presence of the MWCNTs in the membrane changed the microbial diversity in the biofilter cake layer.

Effects of Microplastics and Organic Fertilizer Regulation on Soil Dissolved Organic Matter Evolution.

Microplastics are pollutants of global concern nowadays. However, the effects of microplastics addition to soil as a carbon source and the combined effects of microplastics and organic fertilizer on soil-dissolved organic matter (DOM) evolution are still unclear. This study focused on the evolution of DOM in soil with the addition of microplastics and investigated the variations in the content and composition of DOM in unfertilized and fertilized soil with different particle sizes of microplastics. It was observed that the TOC concentration of the soil DOM in the treatment with organic fertilizer and microplastics increased more (129.97-161.43 mg kg-1) than that in the treatment with microplastics alone (117.17-131.87 mg kg-1) and was higher than that in the original soil (95.65 mg kg-1). According to the humic acid relative abundance in DOM after 40 days of incubation, the humic acid relative abundance in DOM of the soil samples with microplastics and organic fertilizers addition was found to be higher than that in those with microplastic addition alone, reaching more than 80% in a short time. In conclusion, the TOC concentration of the soil DOM increased with the addition of microplastics, and the increase was more pronounced when organic fertilizers and microplastics were added together. Moreover, the soil humification increased to a higher level in the short term with the combined addition of microplastics and organic fertilizers, which was maintained during the long-term incubation process.

Treatment of sludge hydrothermal carbonization wastewater by ferrous/sodium percarbonate system: Effect of wastewater composition and role of coagulation and oxidation

It is crucial to explore the effect of complex wastewater compositions on the ferrous/sodium percarbonate (Fe(Ⅱ)/SPC) system and the role of oxidation-coagulation in designing water treatment processes. This study employed redundancy analysis to investigate the effects of wastewater constituents on oxidation and coagulation. Raman analysis, X-ray Photoelectron Spectroscopy, and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry were used to determine the roles of oxidation and coagulation in the system. The results showed that sulfates and phosphates formed amorphous complexes with iron species via coprecipitation, thereby promoting coagulation to remove organics. Some heavy metals can also be removed by coagulation. The co-activation of SPC by pre-existing transition metals and the added Fe(Ⅱ) facilitated the oxidative removal of organics, while chloride and arsenic were the main inhibitory inorganic substances in the system. Aromatic compounds mainly promoted coagulation, polysaccharides promoted oxidation, humic acid promoted oxidation and coagulation, and C=C/C=O inhibited the Fe(Ⅱ)/SPC system. The oxidation process removed graphitic structures and unsaturated organic matter in the region of (O/C, H/C) = (0.2–0.4, 0.9–2.0) through free radicals and generated amorphous carbon structures and saturated organic matter in the region of (O/C, H/C) = (0.3–0.7, 1.2–1.9). The coagulation process removed aromatic organics with 2–5 rings and unsaturated organics in the region of (O/C, H/C) = (0.2–0.6, 0.7–1.6) with oxygen-containing organics. The combined effects of coagulation and oxidation enhanced the removal efficiency of organic carbon by approximately 40%. This study facilitates the optimization of hydrothermal carbonization wastewater treatment and advanced oxidation processes.

Effect of Humic acid and levels of Zinc and Boron on Chemical Behavior of Zinc in Calcareous Soil

There are global concerns about the significant increase in the concentrations of heavy elements due to the increase in agricultural, urban and industrial activities, which poses a threat to the natural environment and humans. This study focused on studying the addition of humic acid and different levels of zinc on the presence of zinc in the soil in its different forms and its readiness for the plant to find the best concentration and with the presence or absence of humic acid. This study was carried out on the sunflower crop, as zinc was added at levels of (0, 15 and 30) kg h-1 and humic acid at two concentrations, (0 and 50) kg h-1. Zinc was extracted successively and total and available zinc was measured. The results indicated: Concentration of total and available Zinc associated with carbonate minerals, with oxides, and with organic matter in soil increased with increasing levels of Zinc added to soil, reaching 8.638, 1.049, 1.971, 1.658 and 1.625 mg kg-1 soil, respectively. The effect of added humic acid was significant in reducing the concentrations of total Zinc, Zinc bound to carbonate minerals, bound to oxides and residues. The maximum concentrations in case of not adding acid reached 9.313, 1.8957, 1.424, and 4.300 mg kg-1 soil, respectively, while the effect was positively in increasing available concentration associated with organic matter, as concentration in case of adding humic acid reached 0.851 and 1.4584 mg kg-1 soil, respectively. In the case of adding humic acid, this study is considered good for the results it showed in increasing the available zinc with the presence of humic acid, which is reflected in the plant growth and maintaining this element within the recommended concentrations. We determined Zn speciation in the soil system and evaluated the effects of humic acid application on the basic soil properties and Zn bioavailability.

Study of Polymer Ceramic-Inorganic Composites for Electromagnetic Radiation Absorption

The aim of the presented work is to study polymer ceramic-inorganic composites for electromagnetic radiation absorbing. Epoxy-based polymer composites modified with ceramic-inorganic graphite-ferromagnetic (CIGF) fillers were first obtained: silicon carbide, chromium oxide Cr2O3, graphite, humic substances and potassium titanate. As polymer matrix epoxy resin based on Epikote Resin MGS LR 285 and Epikure Curing Agent MGS LH 285 was studied. Primary research was directed to study humic substance, silicon carbide SiC, chromium oxide Cr2O3, graphite and potassium titanate nanoparticles introduction impact on polymer ceramic-inorganic composites strength and technological properties. Complex of technological and strength characteristics were researched and compositions with humic substances 0.5 wt%, a higher silicon carbide SiC – 10 wt% content were studied, while chromium oxide Cr2O3, graphite content in 5–25 % wt. range was optimized. Results shows, that addition of humic substances, silicon carbide SiC, chromium oxide Cr2O3, graphite and potassium titanate nanoparticles into the epoxy resin up to 20 wt% filler content increases the composite impact strength and breaking stress during bending. The CIGF fillers complex system using advantage is proven by studying the nature of modification effect on ceramic-ferromagnetic-graphite polymer composites for electromagnetic radiation absorption.

CoFe2O4-catalytic ceramic membrane for efficient carbamazepine removal via peroxymonosulfate activation

Poor water removal of low-molecular-weight anthropogenic contaminants is always a key problem in low-pressure membrane filtration process. In this work, we successfully designed and fabricated a novel cobalt-based bimetallic catalytic ceramic membrane (CoFe2O4@CM-2) with peroxymonosulfate (PMS) activation and membrane filtration dual functionality, employing a facile impregnation-filtration-calcination method. The resulting CoFe2O4@CM-2/PMS filtration system was specifically tailored for the removal of carbamazepine (CBZ). Our results demonstrate that the CoFe2O4@CM-2/PMS system achieved efficient removal of CBZ from contaminated waters. Under optimal conditions (PMS dosage of 0.5 mM and an operating flux of 40 L·m−2·h−1), the CoFe2O4@CM-2/PMS system exhibited remarkable CBZ removal efficiency, reaching up to 96.5 %. This efficiency was 32.2 and 19.3 times higher than that achieved by ceramic membrane filtration alone and PMS treatment alone, respectively. Additionally, the CoFe2O4@CM-2/PMS system facilitated 37.0 % mineralization of CBZ and up to 87 % utilization of PMS in the permeate. Furthermore, the CoFe2O4@CM-2/PMS system demonstrated robust performance, removing over 91 % of CBZ across a pH range of 3–9 and maintaining stability stability in the presence of humic acid (HA) interference. Its exceptional anti-fouling ability effectively mitigates membrane flux loss compared to single membrane filtration process. Quenching test, electron paramagnetic resonance (EPR), and X-ray photoelectron spectroscopy (XPS) analyses revealed that 1O2, SO4-∙ and ·OH were the primary active substances in the system, while the redox cycle of Co2+/Co3+ played a crucial role in PMS activation. Moreover, the presence of iron (Fe) in the CoFe₂O₄@CM-2 expedited the Co2+/Co3+ cycle and enhanced PMS activation. This study introduces an innovative approach for fabricating ceramic membranes with catalytic degradation capabilities for organic pollutants and suggests promising avenues for integrating separation and advanced oxidation processes (AOPs) in future applications.

Unveiling the effects of dissolved organic matter (DOM) extracted from coastal algae and river on the photooxidation of arsenite

The coastal environment is an important ecosystem connecting land and sea, and arsenite (As(III)) in coastal seawater can seriously affect human health through the food chain. However, the effects of dissolved organic matter (DOM) extracted from coastal algae and rivers on As(III) photooxidation remain unclear. Results show that coastal algal DOM (CA-DOM) is significantly more effective than Suwannee River natural organic matter (SRNOM) in photooxidation of As(III), with a rate 8.3 times higher after correcting for light screening effects. CA-DOM accelerates As(III) photooxidation mainly through the 3DOM⁎ pathway, contributing 78.7 % to the process, whereas 3NOM⁎ contributes only 37.2 % for SRNOM. CA-DOM consists primarily of low-excited tyrosine and tryptophan-like protein substances, whereas SRNOM consists of humic and fulvic acid-like substances. Thus, CA-DOM exhibits a higher steady-state concentration of 3DOM⁎, and the 3DOM⁎ reacts much faster with As(III) than the 3NOM⁎. The increase in CA-DOM concentration can significantly accelerate the photooxidation of As(III), whereas the effect of SRNOM concentration is negligible. Increased salinity can accelerate As(III) photooxidation for all types of DOM. Our results provide new insights into the role of DOM from different sources in the photooxidation of As(III) in the natural environment or engineering applications.

The Effect of Humic Acid Supplementation on Selected Ruminal Fermentation Parameters and Protozoal Generic Distribution in Cows

The objective of this study was to examine the effect of humic acid (HA) supplementation on the rumen fermentation and protozoal community in the rumen. For this purpose, four ruminally cannulated Simmental cows were randomly assigned in a replicated 4 × 4 Latin square design experiment to study the effect of HA dietary supplementation on feed utilization, rumen fermentation, and protozoal community for 84 days. The basal diet (BD) was composed of meadow hay (68.2% of dry matter [DM]), maize silage (17% of DM), and granulated feed mixture (14.9% of DM). There were four treatments, including the BD without additives (control diet, H0), the BD supplemented with 50 g HA/cow/day (H50 treatment), the BD supplemented with 100 g HA/cow/day (H100 treatment), and the BD supplemented with 200 g HA/cow/day (H200 treatment). HA supplementation did not affect the total or individual volatile fatty acid concentrations, the total protozoa, or the ruminal pH. However, HA at the dosage of 50 g/cow/day increased the NH3-N concentration and fecal nitrogen compared to the control (p < 0.001). HA supplementation also significantly impacted the abundance of individual protozoal genera in the rumen. The results of this study suggest that HA has potential in ruminants as a natural feed additive and may play a role in nitrogen metabolism and stabilizing the protozoal community without adverse effects on rumen fermentation.

Soil phosphorus fractionations as affected by cropping systems in the central mid-hills region of Nepal.

Soil plays a critical role as the primary reservoir of phosphorus (P) in terrestrial ecosystems. Sequential fractionation has been extensively utilized to gain insights into the characteristics and dynamics of soil P. However, there is a knowledge gap regarding the different P pools in Nepalese soils. Therefore, this study aimed to investigate the impact of cropping systems on soil P fractions in the central mid-hills of Nepal. The study focused on four cropping systems: vegetable, fruit, rice, and maize-based systems, which exhibited variations in nutrient management, topography, and cropping intensity. A total of 240 soil samples (60 samples from each cropping system) were collected from multiple sites within the central mid-hill region. Standard analytical methods were used to determine the general parameters of the soils, while the sequential fractionation method was employed to assess the organic and inorganic P pools. The results indicated that the effect of cropping systems on soil pH, calcium carbonate (CaCO3) content, and the proportion of sand, silt, and clay was not statistically significant in terms of general parameters. However, significant differences were observed among the different cropping systems in organic matter (OM), electrical conductivity (EC), cation exchange capacity (CEC), and available phosphorus. Similarly, in terms of inorganic phosphorus fractions, loosely bound P (LB-P), aluminum bound P (Al-P), iron bound P (Fe-P), and reductant soluble P (RS-P) were significantly affected, while calcium bound P (Ca-P) did not show a significant difference. Furthermore, in terms of organic phosphorus fractions, labile organic P (L-Po), fluvic acid organic P (FA-Po), and non-labile organic P (NL-Po) exhibited significant differences, whereas moderately labile organic P (ML-Po) and humic acid organic P (HA-Po) did not show a significant difference. Additionally, reductant soluble P showed a significant difference, while total P did not differ significantly. The vegetable-based system exhibited higher levels of the majority of P fractions, followed by the fruit-based, maize-based, and rice-based systems. These findings emphasize the importance of considering cropping systems and their response to different phosphorus pools, as this knowledge can contribute to the development of improved soil phosphorus management strategies and promote sustainable agricultural practices in the region.

The competition of humic acid aggregation and adsorption on clay particles and its role in retarding heavy metal ions

Humic acid (HA) is of great importance in controlling the fate of heavy metals (HMs), however, the pivotal influence of HA aggregation within the HA-clay-HM ternary system on retarding HM mobility remains obscure. This study performed molecular dynamics simulations to delve into the consequences of HA aggregation on the environmental behavior of Cd2+ and Pb2+ (0.1–0.6 M) in the co-existence of illite particles. HA can readily aggregate into clusters, adhering to the illite surface or freely dispersing in the solution. These HA clusters significantly modulate HM mobility, contingent upon their location, arrangement, and interaction with illite. Consequently, HA exhibited a pronounced retardation effect on HM migration, stemming from the competition between HA aggregation and its adsorption on illite. Additionally, the retardation effect of HA aggregation was more obvious for Cd2+ (as compared to Pb2+), owing to its stronger interaction with the functional groups of HA. These findings contribute to the development of potential HA-based strategies for remediation of heavy metal-contaminated sites.

An insight into PANI-TiO2 photocatalysis of refractory organic matter through molecular size fractionation.

Refractory organic matter (RfOM) is ubiquitous in aquatic environment and plays various roles in regulating the fate, transport, toxicity, and bioavailability of chemical species, such as metals, emerging organic contaminants, and nanomaterials. RfOM is mainly represented by humic acids (HA) as the acid insoluble fraction of organic matrix. Considering the complex and multicomponent characteristic of HA, a detailed study was designed to elucidate the fate of molecular size fractions (MSFrs) of humic under solar irradiation in the presence of polyaniline (PANI)-modified TiO2 composites. Humic acid as a consortium of diverse molecular size fractions with different tendencies towards oxidation requires further assessment by UV-vis and fluorescence spectroscopic parameters complementary to previous studies on the photocatalytic degradation of RfOM by using TiO2 and PANI-TiO2 composites. Absorbance-based removal efficiencies under initial and post-photocatalytic conditions showed a re-formation trend during photocatalysis in the presence of PANI and TiO2 where higher MSFrs were transformed to lower MSFrs that was apparent for < 3kDa fraction. Completely different profiles were observed for PT-41 and PT-81 indicating similar degradation pathways independent of PANI ratio in the composite. As confirmed by the investigated parameters, formation of both 450kDa and 220kDa MSFrs were evident under all conditions indicating in situ generation of higher MSFrs. The eligibility of coupled absorbance-fluorescence measurements to discern molecular size distribution of humic acid via oxidative degradation was also investigated. Excitation-emission matrix (EEM) contour plots emphasized the ratio dependency of PANI modification of TiO2 and revealed sample specific variations that were more pronounced in terms of the emergence of tyrosine- and tryptophan-like aromatic proteins.

Influence of dissolved organic matter on U(VI) removal at varying hydrogeochemical scenarios in ultrafiltration process

Uranium (U) is a chemical and radioactive groundwater contaminant that needs to be regulated in drinking water to avoid health hazards. In this study, we have investigated the mechanisms underlying ultrafiltration (UF) process, a low energy-intensive technology, for the removal of uranium from contaminated groundwater, in the presence of dissolved organic matter (i.e. Humic Acid [HA]) under environmentally-relevant conditions representative of regional scenario of Punjab, India. Stirred cell UF experiments with aqueous solutions containing uranium were performed with five different UF membranes with molecular weight cut off (MWCO) ranging from 1 kDa to 30 kDa at a pH of 8.5 that represented ambient groundwater scenario. In the absence of HA, the U(VI) removal was highest for the UF membrane with the lowest MWCO (i.e. 1 kDa) and vice-versa. Further, the effect of various solution parameters viz. pH, concentration of HA, and salinity have been studied using three different UF membranes viz. 5 kDa, 10 kDa, and 30 kDa. Uranium rejection was found to be maximum at pH 5.5 with ca. 97 %, 94 %, and 87 % rejection for 5 kDa, 10 kDa, and 30 kDa membranes, respectively. Further, U(VI) speciation results of the hydrogeochemical model corroborated that the removal of U(VI) in the presence of HA was highly dependent on feed solution pH. Moreover, U(VI) removal increased significantly with an increase in HA concentration, indicating the dominant role of U(VI)-HA complexes. Further, it was observed that increasing the salinity levels to 100 mM in the feed solution (i.e. semi-brackish water scenario) decreased U(VI) rejection primarily due to the charge screening effect. Our results show that using the UF separation process, the World Health Organization’s drinking water guideline value of 30 µg of U L−1 could be achieved in U(VI) contaminated groundwater that contains significant HA levels.

Thermal Catalytic Production of Potassium Humate Fertilizer from Tobacco Straw and Its Performance in Wheat Hydroponics

Production of artificial humic acid (AHA) from waste biomass will contribute to environmental protection and agricultural productivity. However, there is still a lack of a faster, more efficient and eco-friendly way for sustainable production. In this study, potassium humate was prepared from agricultural waste tobacco straw by thermal catalysis using environmentally friendly Fe2O3 as a catalyst. The yield of potassium humate was successfully increased to 68.77 %. In the present study, using characterization methods such as TG-DTG and UV, it was found that the potassium humate prepared from tobacco straw had lower aromaticity, smaller molecular weight, as well as better solubility and better quality. In addition, the effect of potassium humate fertilizer on wheat biomass was also investigated in this experiment by wheat hydroponics. The results showed that the germination rate of wheat increased by 17 % and the fresh and dry weights increased by 6.94 % and 19.31 %, respectively, with the addition of potassium humate prepared with iron catalyst. This study provides a green and simple technology for the resourceful utilization of tobacco straw to produce high value-added potassium humate, and enriches the source of raw materials for potassium humate, expanding its application in the field of crop growth.

Bimetallic complexation for significant fluorescence enhancement of faecal pigment towards water quality testing

Systematic spectroscopic investigations revealed bimetallic complexation of faecal pigments (FP) in waterthrough their multiple binding sites. FP-Zn(II)/Gd(III) complexes showed narrow emission (FWHM ∼ 26 nm) with maximum intensity compared to different bimetallic complexes in water. The fluorescence intensity of bimetallic Zn(II)/Gd(III) complexes of FP increased ∼3–5 fold in aqueous media compared to the FP-Zn(II) complexes, i.e. well-known as Schlesinger’s test. The optimum Zn(II): Gd(III) stoichiometry was observed at 3:2 for maximum FP fluorescence enhancement. The bimetallic FP-Zn(II)/Gd(III) complexes also exhibited higher fluorescence lifetimes and quantum yield than FP-Zn(II) complexes. The photophysical investigations demonstrated that bimetallic Zn(II)/Gd(III) complexation increased the rigidity of chromophores present in FP. Consequently, a decrease in non-radiative decay rate constants (knr) by ∼ 1.5 times was observed for bimetallic complexes compared to FP-Zn(II) in water. Hence, a detection limit of the nanomolar concentration range of FP could be achieved in the aqueous media. The effect of diverse interfering factors (humic acid, water hardness, pH) on the fluorescence behaviour of FP-Zn(II)/Gd(III) complexes was also investigated with an approach mimicking real water samples. Finally, a simple non-extraction analytical approach for sensitive detection of FP in water was demonstrated while also considering the fluorescence matrix interference problem.

Research on Composting of Garden Waste and Its Application in Cultivation Substrates

To achieve the resource utilization of garden waste, in this study, we used garden waste as the main raw material and conducted static composting with high-temperature aerobic treatment and forced ventilation by adding appropriate external additives. Our results showed that during the composting process, the pH was weakly alkaline, and the electrical conductivity was between 1.42 and 1.50 mS/cm. The E4/E6 (an important indicator of the quality or degree of condensation and aromatization of humic acid) gradually decreased, and nitrogen, phosphorus, and potassium contents increased. The germination index gradually rose and ultimately exceeded 80%. Treatment (T2) with a final C/N ratio of 25:1 and the addition of 0.3% bacterial agent resulted in the highest nutrient content and the best degree of compost maturity. All indicators met the requirements of the Chinese “Technical Requirements for Urban Landscape Waste Resource Recycling and Deep Processing (GB/T 40199-2021)”. When using a composite substrate of garden waste and other horticultural substrates for planting, a membership function was executed for comprehensive evaluation. The V (T2):V (peat):V (vermiculite):V (vermiculite) = 135:135:30:00 substrate treatment resulted in optimal lettuce growth and quality. In summary, combining the compost products of garden waste with traditional cultivation substrates at a specific ratio shows favorable applicative prospects.

Regulation of the co-transport of toluene and dichloromethane by adsorbed phase humic acid under different hydro-chemical conditions

The transport behavior of combined organic pollutants in soil and groundwater has attracted significant attention in recent years. Research on the influence of humic acid (HA) on organic pollutant transport behavior mainly focuses on the study of the mobile phase HA, with less research on the adsorbed phase HA, especially regarding its interaction with combined pollutants. To enhance understanding of the regulation of co-transport and retention of combined pollutants by adsorbed phase HA, in this study, tests were conducted to investigate how toluene (TOL) and dichloromethane (DCM) are transported in the presence of adsorbed phase HA at different pH levels and ionic strengths. As the proportions of HA-coated sand increased, so did its adsorption capacity for TOL and DCM, which can be attributed to adsorbed phase HA providing more adsorption sites compared to plain sand, thereby reducing the transport potential of the pollutants. The presence of both TOL and DCM facilitated their mutual transportation due to competitive adsorption controlled by the adsorbed phase HA content in the porous medium. Furthermore, it was observed that pH levels influenced the transport behavior of TOL and DCM when adsorbed phase HA was present since adsorbed phase HA transformation into mobile phase was regulated by pH levels. The transport patterns can be effectively simulated using the chemical nonequilibrium two-site sorption model in HYDRUS-1D, accurately reflecting the retardation coefficients and transport distances based on model parameters. This work sheds new light on the regulatory role of adsorbed phase HA in TOL and DCM transport under diverse hydrochemical conditions, with implications for accurately depicting the behavior of combined pollutants, optimizing the remediation strategies and improving remediation efficiency in contaminated sites.

Biogenic amorphous FeOOH activated additional intracellular electron flow pathways for accelerating reductive dechlorination of tetrachloroethylene

Dissimilatory iron-reducing bacteria (DIRB) with extracellular electron transfer (EET) capabilities have shown significant potential for bioremediating halogenated hydrocarbon contaminated sites rich in iron and humic substances. However, the role and microbial molecular mechanisms of iron-humic acid (Fe-HA) complexes in the reductive dehalogenation process of DIRB remains inadequately elucidated. In this study, we developed a sustainable carbon cycling approach using Fe-HA complexes to modulate the electron flux from sawdust (SD), enabling almost complete reductive dechlorination by most DIRB (e.g., Shewanella oneidensis MR-1) that lack complex iron-sulfur molybdo enzymes. The SD-Fe-HA/MR-1 system achieved a 96.52% removal efficiency of tetrachloroethylene (PCE) at concentrations up to 250 μmol/L within 60 days. Material characterization revealed that DIRB facilitated the hydrolysis of macromolecular carbon sources by inducing the formation of amorphous ferrihydrite (FeOOH) in Fe-HA complexes. More importantly, the bioavailable FeOOH activated additional intracellular electron flow pathways, increasing the activity of potential dehalogenases. Transcriptome further highlight the innovative role of biogenic amorphous FeOOH in integrating intracellular redox metabolism with extracellular charge exchange to facilitate reductive dechlorination in DIRB. These findings provide novel insights into accelerating reductive dechlorination in-situ contaminated sites lacking obligate dehalogenating bacteria.

Responses of soil microbial metabolism, function and soil quality to long-term addition of organic materials with different carbon sources

Biochar and green manure have been widely applied in agricultural production and are important means to achieve sustainable agriculture. However, there is limited research systematically and comprehensively exploring the response of soil microbiota and the changes in soil metabolomics after the addition of two different carbon source amendments to the soil, and the differential mechanisms of soil metabolomics between them remain unclear. In this study, a long-term field experiment (initiated in 2019) was conducted to investigate the effects of biochar and green manure application on soil nutrients and soil functions driven by soil microbes. Compared to the pure fertilizer treatment, biochar increased soil total carbon by 14.54% to 27.04% and soil available potassium by 4.67% to 27.46%. Ryegrass significantly increased soil available phosphorus and organic matter. Under different fertilization regimes, the ecological niches of soil microbes changed significantly. Network analysis revealed that long-term ryegrass returning reduced the complexity of soil microbial networks. Ryegrass and biochar increased dispersal limitation in fungal assemblages (reaching 93.33% and 86.67%, respectively), with biochar particularly enhancing variable selection in bacterial assemblages (accounting for 53.33%). Variation partitioning analysis based on redundancy analysis indicated that humic substances had the highest explanatory power for microbial community variation, with humic substances explaining 38.49% of bacteria and 52.19% of fungi variation. The ryegrass treatment mainly changed the abundance of carbohydrates (CH), amines (AM), c (AH), and lipids (LP), while the BC treatment mainly altered the abundance of organic acids (AC), amines (AM), and carbohydrates (CH). Meanwhile, both treatments significantly reduced the bisphenol A, one of the soil pollutants. Ryegrass incorporation significantly increased the abundance of genes related to soil C, N, P, and S cycling, especially genes involved in carbon decomposition, while biochar significantly enhanced the abundance of nitrogen fixation genes nifH and Hao in soil. Random forest model results indicated that carbohydrates, alcohols, aromatics (AR), and ester (ES) were the main categories of metabolites in soil influenced by differential microbes, and Finegoldia served as a common important metabolic driving species. In summary, this study reveals the processes of soil function, microbial community succession, and metabolism driven by ryegrass and biochar, providing important insights for optimizing soil management and improving soil quality.Graphical

Revealing the vital role of sulfur site on the surface of pyrite in 1O2 formation for promoting ciprofloxacin degradation via peracetic acid activation

Pyrite has been widely utilized to activate oxidants for water treatment, yet the regulation of reactive oxygen species (ROS) by sulfur sites on its surface has been overlooked. In this study, the surface sulfur sites were regulated by thermal modification of natural pyrite in the N2 atmosphere (denoted as P-X, where X represented pyrolysis temperatures ranging from 400 to 700 °C), and these modified pyrites were employed to activate peracetic acid (PAA) for ciprofloxacin (CIP) degradation. The results revealed that the degradation rate of CIP increased as the reduced sulfur content increased, with the P600/PAA system achieving the highest apparent degradation rate (kobs = 0.0999 min−1). Quenching experiments and electron paramagnetic resonance (EPR) analysis identified various ROS involved in the P-X/PAA system, with hydroxyl radical (·OH) and singlet oxygen (1O2) identified as dominant reactive species responsible for CIP degradation. The reduced sulfur sites served as the primary active sites facilitating the conversion of organic radicals (·CH3C(O)OO) into superoxide radicals (·O2−) and 1O2. Furthermore, the P600/PAA system demonstrated robust adaptability under both acidic and neutral pH conditions, efficiently degrading CIP even in the presence of complex matrices such as Cl−, NO3−, SO42−, NH4+, or humic acid (HA) in water bodies, although HCO3− was found to inhibit CIP degradation. This study significantly enhances our understanding of the interaction between reduced sulfur sites and ROS in PAA-based advanced oxidation processes (AOPs), offering a promising technology for efficient antibiotic treatment in water purification.

Vanadium (V) reduction and the performance of electroactive biofilms in microbial fuel cells with Shewanella putrefaciens

The electron transfer ability of biofilms significantly influences the electrochemical activity of microbial fuel cells (MFCs). However, there is limited understanding of pentavalent vanadium (V(V)) bioreduction and microbial response characteristics in MFCs. In this study, the effect of gradient concentrations of V(V) on the performance of EABs with Shewanella putrefaciens in MFCs was investigated. The results showed that as V(V) concentration increased (0–100 mg/L), the voltage output, power densities, polarization, and electrode potential decreased. V(V) was found to act as an electron acceptor and was reduced during MFCs operation, with a yield of 83.16% being observed at 25 mg/L V(V). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) indicated declining electrochemical performance of the MFCs with escalating V(V) concentration. The content of protein and polysaccharide from extracellular polymeric substances (EPS) in anodic biofilms increased to 66.75 and 49.15 mg/L at 75 mg/L V(V), respectively. Three-dimensional fluorescence spectroscopy confirmed increased humic substances in EPS extraction with V(V) exposure. The functional genes narG, nirK, and gor involved in V(V) reduction were upregulated with rising V(V) concentration through quantitative polymerase chain reaction (qPCR) analysis. Additionally, riboflavin, cytochrome c, nicotinamide adenine dinucleotide (NADH), and electron transport system activity (ETSA), key indicators for assessing electron transfer behavior, exhibited a negative correlation with various V(V) concentrations, decreasing by 31.81%, 57.14%, 67.39%, and 51.41%, respectively, at a concentration of 100 mg/L V(V) compared to the blank control. These findings contribute valuable insights into the response of EABs to V(V) exposure, presenting potential strategies for enhancing their effectiveness in the treatment of vanadium-contaminated wastewater.