High Humic Acid Research Articles

Adding Humic Acids to Gelatin Hydrogels: A Way to Tune Gelation.

Exploring the chance to convert biowaste into a valuable resource, this study tests the potential role of humic acids (HA), a class of multifunctional compounds obtained by oxidative decomposition of biomass, as physical agents to improve gelatin’s mechanical and thermal properties. To this purpose, gelatin–HA aqueous samples were prepared at increasing HA content. HA/gelatin concentrations changed in the range 2.67–26.67 (wt/wt)%. Multiple techniques were employed to assess the influence of HA content on the gel properties and to unveil the underlying mechanisms. HAs increased gel strength up to a concentration of 13.33 (wt/wt)% and led to a weaker gel at higher concentrations. FT-IR and DSC results proved that HAs can establish noncovalent interactions through H-bonding with gelatin. Coagulation phenomena occur because of HA–gelatin interactions, and at concentrations greater than 13.33 (wt/wt)%, HAs established preferential bonds with water molecules, preventing them from coordinating with gelatin chains. These features were accompanied by a change in the secondary structure of gelatin, which lost the triple helix structure and exhibited an increase in the random coil conformation. Besides, higher HA weight content caused swelling phenomena due to HA water absorption, contributing to a weaker gel. The current findings may be useful to enable a better control of gelatin structures modified with composted biowaste, extending their exploitation for a large set of technological applications.

Evaluation of membrane tailored with biocompatible halloysite‒polyaniline nanomaterial for efficient removal of carcinogenic disinfection by‒products precursor from water

Humic acid (HA) is the main component of natural organic matter that generates carcinogenic by‒products during disinfection and its removal from water resources is challenging. Biocompatible halloysite (HNTs) nanomaterial decorated with polyaniline (HNTs‒PANI) was synthesized via polymerization technique. HNTs‒PANI was added to prepare polyethersulfone mixed matrix membranes (MMMs). The influence of HNTs‒PANI concentration on HA removal efficiency was studied by varying the HNTs‒PANI (0.5, 1 and 1.5 wt%). The characterization studies of MMMs revealed that the addition of HNTs‒PANI improved the morphology of the membranes, surface properties, chemical stability and thermal property. The amine and hydroxyl groups within the MMMs improved the membrane wettability. The addition of HNTs‒PANI within the MMMs had significantly enhanced the pure water flux and HA filtration. YHP2 MMM with 1 wt% of HNTs‒PANI demonstrated sieving coefficient of 0.10 and the highest HA removal efficiency of 91% greater than the neat PES membrane. Furthermore, the antifouling property of the MMMs was studied using HA as foulant. 1 wt% of HNTs‒PANI added MMM showed a high flux recovery ratio (94.9%) with low total fouling of 12% and low irreversible fouling of 5%, respectively. Thus, HNTs‒PANI was an efficient nanomaterial for enhancing the pure water flux, removal efficiency and antifouling property to treat water contaminated with HA.

Stability of humic acid carbon under conservation agriculture practices

Recently conservation agriculture (CA) using the principles of zero tillage, crop residue management and suitable crop rotation has gained the momentum and quite popular among the farmers. Researchers throughout the globe have shown the potential of CA in enriching soil organic carbon storage in various soil types and cropping systems. But there is very limited study on the effect of CA on soil humic acid content and their stability and abundance of functional groups. An experiment was conducted in an Alfisols with four scenarios (designated as Sc) namely conventional farmers practice (Sc1) of transplanted rice (TPR) followed by conventional tilled broadcasted wheat (CT- wheat) with residue removal, transplanted rice (TPR) followed by zero tillage (ZT) wheat and mung bean with partial residue retention (Sc2), direct seeded rice (DSR) followed by ZT- wheat and mung bean with full residue retention (Sc3), ZT-maize followed by ZT-wheat and mung bean (Sc4) at the research farm of ICAR-Central Soil Salinity Research Institute, Karnal, Haryana, India. The objectives of this study were to assess the humic acid (HA) content and stability of soil carbon through desorption study and to characterize the functional groups of HA by Fourier Transform Infrared (FTIR) spectroscopy under different scenarios. HA was extracted from soil samples collected from 0 to 15 and 15–30 cm depth after rice harvesting in 2018 after nine years of the experiment. Results showed that Sc4 recorded significantly highest HA content at 0–15 depth (4.23 g/kg) and 15–30 cm soil depth (2.08 g/kg). Lower E4/E6 ratio revealed higher stability and humification of humic acid carbon under CA based scenarios. Lowest desorption rate constant (0.20/day) was observed under Sc4 indicating higher organic carbon stability in soil. Higher labile carbon and nitrogen was observed in soils under Sc3 as revealed through desorption study. FTIR spectroscopy results confirmed the prevalence of higher number of functional groups (OCO, CO or CHO) in HA under CA based scenarios with an order of Sc4 >Sc3 >Sc2 >Sc1. Therefore, CA is not only efficient in enriching the organic carbon in soil but also in more stable complex of HA with soil particles having long term implications in soil carbon sequestration for future posterity.

Mechanistic Insight into Humic Acid-Enhanced Hydroxyl Radical Production from Fe(II)-Bearing Clay Mineral Oxygenation.

Hydroxyl radical (•OH) production by electron transfer from Fe(II)-bearing clay minerals to oxygen has been increasingly reported. However, the influence of ubiquitous coexisting humic acid (HA) on this process is poorly understood. Here, we investigated the effect of different HA on •OH production during the oxygenation of reduced nontronite NAu-2 (rNAu-2), montmorillonite, and sediment. Results showed that HA could enhance •OH production, and the enhancement was related to the content of reactive Fe(II) in rNAu-2 and the electron-accepting capacity of HA. Coexisting HA leads to a new electron-transfer pathway from Fe(II) in rNAu-2 to HA (instead of the HA-Fe complex) and then to O2, changing the first step of O2 reduction from one- to two-electron transfer process with H2O2 as the main intermediate. Reduced HA decomposes H2O2 to •OH at a higher yield (13.8%) than rNAu-2 (8.8%). Modeling results reveal that the HA-mediated electron-transfer pathway contributes to 12.6-70.2% of H2O2 generation and 13.2-62.1% of •OH formation from H2O2 decomposition, with larger contributions at higher HA concentrations (5-100 mg C/L). Our findings implicate that HA-mediated electron transfer can expand the area of •OH production from the mineral surface to the aqueous phase and increase the yield of •OH production.

Micro-gel thin film molecularly imprinted polymer coating for extraction of organophosphorus pesticides from water and beverage samples

Molecularly imprinted polymers (MIPs) have become an important class of materials for selective and efficient adsorption of target analytes. Despite versatility of MIPs for fabrication in numerous formats, these materials have been primarily reported as solid phase extraction packing materials. An effective thin film MIP prepared on stainless steel substrate is reported here for high throughput enrichment of organophosphorus pesticides (OPPs) from water and beverage samples followed by liquid chromatography tandem mass spectrometry (LC-MS/MS) analysis. The key factors controlling performance as well as best practices for optimized fabrication of thin film MIPs are presented. A pseudo-phase diagram is introduced to evaluate and predict the effect of the ratio of porogen (solvent, 1-octanol) volume to relative crosslinker mass on the desired polymer features (i.e., porosity, surface area, capacity, and selectivity). At low porogen ratios, a macroporous polymer with insignificant selectivity is formed, whereas at high porogen ratios a micro-gel polymer with superior selectivity towards targets is obtained. The porosity and morphology determined with nitrogen adsorption and scanning electron microscopy were attributed to specific regions in the pseudo-phase diagram. Other factors influencing selectivity and stability of the polymer, such as type of the template and its ratios with monomer (methacrylic acid) and crosslinker (ethylene glycol dimethacrylate) were optimized. The prepared thin film MIPs were characterized using adsorption isotherms and adsorption kinetics, and evaluated for matrix effects (high humic acid content) and cross-reactivity in presence of other pesticides and pharmaceuticals. The optimized method provided limits of quantitation (LOQs) ranged from 0.002 to 0.02 ng mL−1 in water and from 0.095 to 0.48 ng g−1 in apple juice. Regarding inter-device variability (CV∼10% without normalization), excellent linearity (R2 > 0.99), satisfactory accuracies (90–110%) and precisions (<15%) were obtained.

Removal of Humic Acid Using 3-Methacryloxypropyl Trimethoxysilane Functionalized MWCNT Loaded TiO2/PES Hybrid Membrane.

In the present work, a highly efficient mixed matrix membrane (MMM) for humic acid (HA) removal was developed. Multiwalled carbon nanotubes (MWCNTs) were functionalized in the presence of 3-methacryloxypropyl trimethoxysilane using the co-condensation method and were subsequently loaded with TiO2 (prepared via the sol–gel route). The as-prepared material was then incorporated into a PES polymer solution to prepare a fMWCNT-TiO2/PES hybrid membrane via non-solvent induced phase inversion. The microstructure of the membrane was characterized using Fourier transform infrared spectroscopy, atomic force microscopy, scanning electron microscopy, water contact angle, thickness, porosity, and pore size. The fMWCNT-TiO2/PES hybrid membrane was tested for the removal of HA and antifouling performance. The results show that the surface hydrophilicity of the membranes was greatly improved upon the addition of the fMWCNT-TiO2 particles. The results show that 92% of HA was effectively removed after 1 h of filtration. In comparison with pristine membrane, the incorporation of fMWCNT-TiO2 nanoparticles led to enhanced pure water flux (99.05 L/m2 h), permeate flux (62.01 L/m2 h), higher HA rejection (92%), and antifouling improvement (RFR: 37.40%, FRR: 86.02%). Thus, the fMWCNT-TiO2/PES hybrid membrane is considered to be a great potential membrane for the improvement of ultrafiltration membranes.

Effect of coagulation treatment on antifouling properties of PVC nanocomposite membrane in a submerged membrane system for water treatment

A submerged membrane system was used in this work to investigate the effect of the polyaluminum chloride (PAC) coagulant on the antifouling performance of the polyvinyl chloride/alumina (PVC/Al2O3) nanocomposite membrane. The prepared nanocomposite membranes were characterized with field emission scanning electron microscopy (FE-SEM), atomic force microscopy, contact angle, porosity measurement, and pure water flux. The results revealed that the membrane containing Al2O3 nanoparticles (the mass ratio of PVC to Al2O3 was 98.5/1.5) had a higher hydrophilicity, porosity, and pure water flux than other membranes. The FE-SEM images showed that when Al2O3 nanoparticles were present in the PVC membrane, large pores and macrovoids formed on the surface and cross-section of the membrane. The fouling behavior of membranes was investigated through the filtration of humic acid (HA) solution with and without the PAC coagulant. Without PAC addition, the PVC/Al2O3 membrane significantly decreased the irreversible fouling ratio from 60.7% to 19.4% and showed a high HA removal efficiency of approximately 90.5%. The Hermia model confirmed that the cake formation mechanism best described the experimental data for the neat PVC and nanocomposite membranes with the presence and absence of the PAC coagulant. This confirms that the PAC coagulant can significantly mitigate fouling and improve HA removal in the submerged membrane system.

Removal of Polymerase Chain Reaction Inhibitors by Electromembrane Extraction.

Polymerase chain reaction (PCR) technology has become the cornerstone of DNA analysis. However, special samples (e.g., forensic samples, soil, food, and mineral medicine) may contain powerful PCR inhibitors. High levels of inhibitors can hardly be sufficiently removed by conventional DNA extraction approaches and may result in the complete failure of PCR. In this work, the removal of PCR inhibitors by electromembrane extraction (EME) was investigated for the first time. To demonstrate the universality of the approach, EME formats with and without supported membranes (termed parallel-EME and μ-EME, respectively) were employed, and both anionic [humic acid (HA)] and cationic (Ca2+) PCR inhibitors were used as models. During EME, charged inhibitors in the sample migrate into the liquid membrane in the presence of an electric field and might further leech into the waste solution, while PCR analytes remain in the sample. After EME, the clearance values for HA at 0.2 and 2.5 mg mL-1 were 94 and 85%, respectively, and that for Ca2+ (275 mM) was 63%. Forensic PCR-short tandem repeat (PCR-STR) genotyping showed that EME significantly reduced the interference by HA in PCR-STR analysis and displayed a higher HA purge capability compared to existing methods. Furthermore, by combining EME with liquid-liquid extraction or solid-phase extraction, satisfactory STR profiles were obtained from HA-rich blood samples. In addition, false-negative reports of bacterial detection in mineral medicine and shrimps were avoided after the removal of Ca2+ by μ-EME. Our research demonstrates the great potential of EME for the purification of DNA samples containing high-level PCR inhibitors and opens up a new application direction for EME.

Development of Lignin-Based Mesoporous Carbons for the Adsorption of Humic Acid.

There is an increasing urge to make the transition toward biobased materials. Lignin, originating from lignocellulosic biomass, can be potentially valorized as humic acid (HA) adsorbents via lignin-based mesoporous carbon (MC). In this work, these materials were synthesized for the first time starting from modified lignin as the carbon precursor, using the soft-template methodology. The use of a novel synthetic approach, Claisen rearrangement of propargylated lignin, and a variety of surfactant templates (Pluronic, Kraton, and Solsperse) have been demonstrated to tune the properties of the resulting MCs. The obtained materials showed tunable properties (BET surface area: 95–367 m2/g, pore size: 3.3–36.6 nm, VBJH pore volume: 0.05–0.33 m3/g, and carbon and oxygen content: 55.5–91.1 and 3.0–12.2%, respectively) and good performance in terms of one of the highest HA adsorption capacities reported for carbon adsorbents (up to 175 mg/g).

Eco-environmental preparation of magnetic activated carbon modified with 3-aminopropyltrimethoxysilane (APTMS) from sawdust waste as a novel efficient adsorbent for humic acid removal: Characterisation, modelling, optimisation and equilibrium studies

ABSTRACT The aim of the present study was to prepare the modified magnetic activated carbon from sawdust (AC/Fe3O4@SiO2-APTMS) as a novel adsorbent for efficient removal of humic acid (HA) from aqueous solutions. The adsorbent was characterised by BET, SEM, FTIR, VSM, and EDS analysis. The optimal values of independent variables were determined using Box-Behnken design based on the response surface methodology (RSM). The maximum HA adsorption of 97.85% was obtained at optimal conditions pH 3, the adsorbent dose 2 g/L, and the contact time 25 min. Analysis of the adsorption data by isothermal, kinetic, and thermodynamic models showed that the adsorption data followed the Langmuir isotherm (R2 = 0.9850) and the pseudo-second-order kinetic model (R2 = 0.9999). The adsorption process was spontaneous and endothermic. The adsorbent regeneration proved high HA removal efficiency after 4 adsorption cycles. The humic acid adsorption behaviour of the adsorbent supports its performance to remove organic contaminants from aqueous solutions.

Arsenopyrite weathering in acidic water: Humic acid affection and arsenic transformation

Arsenopyrite is a common metal sulfide mineral and weathers readily in the open environment, releases As, and pollutes the surrounding environment. Humic acid (HA) is ubiquitous in soils, sediments and waters, and contains various functional groups and complex with arsenic, iron and other metal ions that affect the weathering behavior of arsenopyrite. Because As, iron, and HA are redox-active compounds, electrochemical techniques, including polarization curves, electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV), were used to fundamentally investigate the weathering process and mechanism of arsenopyrite over a wide range of environmental relevant conditions. Polarization curves showed higher HA concentrations (0-1000 mg•L−1), higher temperatures (5-35°C) or acidities (pH 1.0-7.0) promoted arsenopyrite weathering; there was a linear relationship between the corrosion current density (icorr), temperature (T) and acidity (pH): icorr = -3691.2/T + 13.942 and icorr = -0.2445pH + 2.2125, respectively. Arsenopyrite weathering readily occurred in the presence of HA as confirmed by its activation energy of 24.1 kJ•mol−1, and EIS measurements confirmed that the kinetics were controlled by surface reaction as confirmed by decreased double layer resistance. CV and surface characterization (FTIR and XPS) showed that arsenopyrite initially oxidized to S0, As(III) and Fe2+, then S0 and Fe2+ were ultimately converted into SO42− and Fe3+, while As(III) oxidized to As(V). Furthermore, the carboxyl (–COOH) and phenolic (–OH) of HA could bind with As(III)/(V) and Fe3+ via a ligand exchange mechanism forming As(III)/(V)-HA and As(III)/(V)-Fe-HA complexes that hinders the formation of FeAsO4 and decreases the bioavailability of As. Findings gained from this study are valuable for the understanding of the fate and transport of As in acidic conditions, and have powerful implications for the remediation and management of As-bearing sites affected by mining activities.

Enhanced removal of humic acid from aqueous solution by combined alternating current electrocoagulation and sulfate radical.

Application of alternating current in electrocoagulation and activation of persulfate (AEC-PS) for the effective removal of humic acid (HA) from aqueous solution was evaluated. In order to optimize the removal efficiency HA by the AEC-PS process, several influencing parameters such as pH, reaction time, PS dose, current density (CD), concentration of NaCl, initial concentration of HA, and coexisting cations and anions influence were investigated. From the batch experiments, the highest HA removal efficiency obtained was 99.4±0.5% at pH of 5, reaction time of 25min, CD of 4.5mA/cm2, PS dose of 200mg/L, and NaCl concentration of 0.75g/L for an initial HA concentration of 30mg/L. When CD increased from 1.25 to 4.5mA/cm2, the HA removal efficiency was improved from 88.8±4.4% to 96.1±1.5%. In addition, the type of coexisting cations and anions exerted a significant role, leading to a reduction in the removal efficiency of HA. To investigate the dominant free activated radical, radical scavengers such as tert-butyl alcohol and ethanol were employed. It was observed that both OH and SO4- radicals substantially contributed to the removal of HA, and the contribution of SO4- radical was higher than that of OH radical, suggesting that AEC-PS process could serve as a novel and effective treatment technique for the removal of organic matters from aqueous sources.

Investigation of extracellular polymeric substances (EPS) in four types of sludge: Factors influencing EPS properties and sludge granulation

Extracellular polymeric substances (EPS) released by bacteria play a crucial role in microbial aggregation during wastewater treatment. Various environmental factors including substrate, anaerobic and aerobic conditions might contribute to the formation and properties of EPS, and thereby affect the properties of microbial aggregation and sludge. To reveal the relationship between these environmental factors and EPS properties, the characteristics of EPS generated in four types of sludge were investigated, including anammox granular sludge (ANMX), aerobic granular sludge (AGS) fed with glucose as carbon source (AGS-GLUC), AGS fed with liquor wastewater as carbon source (AGS-LIQ), and flocculent sludge from a real sewage plant (FLOC). Results indicated a positive correlation of EPS contents with granulation of sludge. As the dominant content of EPS, an increased proteins (PN) concentration facilitated the formation of microbial aggregates and the granulation of sludge. Bacteria in anaerobic environment (i.e., ANMX) or in aerobic environment with easily biodegradable carbon sources (i.e., AGS-GLUC) would generate more PN and EPS; yet, these conditions restrained the generation of humic acid (HA). The sludge from the sewage treatment plant (i.e., FLOC) had the lowest EPS and PN content, but the highest HA, showing flocculent structure sludge. In addition, a higher protein/polysaccharide (PN/PS) ratio and a lower zeta potential of EPS were conductive to sludge granulation. The hydrophobicity of EPS confirmed via analysis of chemical structures by FTIR would improve the microbial aggregation.

Heteroaggregation of humic acid with montmorillonite in divalent electrolytes: effects of humic acid content and ionic concentration

Clay-humic substance complexes play a major role in controlling the mobility of elements and colloids in natural soils. The purpose of the present study is to explore the different reaction mechanisms induced by cations on the humic acid (HA) and montmorillonite (Mt) heteroaggregation and to analyze the binding mechanism of HA-Mt. HA is extracted from soil and colloidal Mt are prepared as K+-saturated. The aggregation kinetics of HA-Mt composite nanoparticles in Ca(NO3)2, Mg(NO3)2, and Cu(NO3)2 solutions were detected by dynamic light scattering. Furthermore, FT-IR spectroscopy was used to characterize the reactive sites involved in interaction with the metal ions. The results revealed that the order of reaction of these three metal cations with the HA-Mt composite was Cu2+ > Ca2+ > Mg2+, as evident from the total average aggregation rate, critical coagulation concentration, and activation energy. The heteroaggregation process was sensitive to the 1% mass percentage of HA; however, more HA (4% mass percentage) did not significantly affect this process compared with 1% HA. Higher cation concentration and higher HA content (10% mass percentage) were two necessary conditions for promoting HA-Mt heteroaggregation. The vibration peak intensities of the carboxyl group C-O bonds and hydroxyl group O-H bonds of HA were affected by the formation of coordinate bonds with different metal ions. Metal cations were preferentially complexed by the carboxyl groups of HA, and due to its polarization-induced and electric field–enhanced oxidizing properties, Cu2+ has the strongest aggregation ability for HA-Mt, followed by Ca2+ and Mg2+. The HA-Mt heteroaggregation is partially reversible by adjusting electrostatic repulsion. The results of this study improve our understanding of the roles of cations and HA in clay-humic substance interactions.

Effects of different types of humic acid isolated from coal on soil NH3 volatilization and CO2 emissions

Humic acid can improve soil nutrients and promote plant growth. Weathered coal and lignite can be used as agricultural resources due to high humic acid content, but their impact on soil NH3 volatilization and CO2 emissions are yet to be determined. In this study, a field experiment was carried out to compare the effects of four types of humic acid isolated from coal (pulverized weathered coal (HC), pulverized lignite (HL), alkalized weathered coal (AC) and alkalized lignite (AL)) on NH3 volatilization, CO2 emissions, pH, the C/N ratio and enzyme activities in soil cultivated with maize. The effect of biotechnology humic acids (BHA) was also examined for comparison. HL, AC, AL and BHA all increased cumulative NH3 losses by 147.7, 278.5, 113.9, and 355.3%, respectively, compared with the control (chemical fertilizer only), and notably, BHA caused an increase of 90.71% compared with the humic acids isolated from coal. A significant increase in cumulative CO2 losses was observed only under AL treatment, by 14.44–24.90% compared with all other treatments. Soil urease activity was positively correlated with cumulative NH3 losses (P < 0.001), while the soil C/N ratio (P < 0.001) and soil sucrase activity (P < 0.05) were positively correlated with cumulative CO2 losses. Since humic acid from pulverized weathered coal caused no increase in NH3 volatilization or CO2 emissions, it is therefore thought to be the most suitable humic acid for field application.

Effect of Humic Acid on Oxidative Stress and Neuroprotection in Traumatic Spinal Cord Injury: An Experimental Study.

Traumatic spinal cord injury (TSCI) is an important health problem especially in developing countries with additional socio-economic loss. Humic acids (HA) usually have anti-oxidant, anti-inflammatory, blood-circulating and antiviral effects. We aimed to show effect of HA on neuroprotection in TSCI model. We performed TSCI model in Twenty-four Wistar-Albino rats in four groups. Control group underwent only laminectomy. Sham group underwent laminectomy followed by TSCI. Low dose HA (5mg/kg) and high dose HA (10mg/kg) groups underwent laminectomy and TSCI followed by peritoneal administration of HA. Preoperative, postoperative 1st hour and postoperative 24th hour cardiac blood samples were obtained. Total Antioxidant Status (TAS), Total Oxidant Status (TOS) and Oxidative Index (OI) levels were evaluated in serum. The 24th hour motor functions were evaluated by Modified Tarlov Score. There were no significant changes in TAS values between sham- low dose and high dose humic acid groups (p:0.77/0.21). However there were a significant decrease of TOS levels in the 24th hour post operative blood samples comparing the sham group with low dose humic acid group (p=0.02). Pathological evaluation showed a significant decrease in the severity of edema, hemorrhage, Polymorphonuclear leucocytes (PNL) and Mononuclearleucocytes (MNL) /macrophage/microglia when we compare with the control group (p<0.05). There is a significant recovery in paraplegia level as we compared the HA groups with control groups (p<0.001). In this study, we showed the effects of HA in the early stages of TSCI on oxidative stress, histopathological changes and neurological improvement. It is thought to be a potential therapeutic agent in acute TSCI but needs to be further evaluated by showing proper effect on other neuroprotective pathways in larger series.

Improvement of moss photosynthesis by humic acids from Antarctic tundra soil

There have been several published reports regarding the growth promoting effect of humic acids (HA) on vascular plants; however, the effect of HA on bryophytes is still unknown. Due to the ecological importance of mosses, which dominate the Antarctic flora, we assessed the effectiveness of HA as a biostimulant using three moss species: Antarctic Ceratodon purpureus KMA5038, Arctic Bryum sp. KMR5045, and Physcomitrella patens which inhabits temperate regions. Natural HA (KS1-3_HA) were extracted through acidic precipitation of alkaline extracts from Antarctic tundra soil. Spectroscopic structural properties of KS1-3_HA were characterized and determined to possess several functional groups such as hydroxyl (R–OH) and carboxyl (R–COOH), implying they could have a growth-related biological function. For two polar mosses, increasing HA concentrations correlated with increased growth and photosynthesis. The efficiency for temperate moss increased at lower concentrations tested, but rather began to reduce at the highest HA concentration, indicating that effective concentrations of HA vary depending on the moss species and habitat. Based on these results, Antarctic HA may have ecological role in enhancing the growth and photosynthesis of Antarctic mosses. We believe this is the first study to establish a positive physiological effect of HA on mosses and hope it may serve as a basis for studying the role of HA in preserving the terrestrial ecosystem of Antarctica.

The NMR and spectral study on the structure of molecular size-fractionated lignite humic acid

In this study, high pure humic acid (HA) extracted from lignite was fractionated into four fractions according to their molecular weights by the ultrafiltration method. The structural characteristics of various HA fractions were investigated by UV–Vis,FTIR, and 3D fluorescence spectra and 13 C/ 1 H-NMR tests. The experiment results showed that the HA fractions with the molecular weight ＞50 KDa are major, containing 70.89%. The active hydrogen proportion declined from 43.96% to 21.27% with the increase of HA molecular weight, meaning the decrease of the large HA molecules’ acidic group content. On the other hand, 80.93% of the aromatic nucleus content and 12.5% of the alkyl carbon (aliphatic structure) were observed in the large HA molecules that are much higher than those in the small HA molecules. The NMR and spectra studies indicated that the small HA molecules have more acidic groups such as hydroxy, carboxyl. Meanwhile, the large HA molecules have more aromatic and aliphatic structures. The above research indicated that the HA fractions with low molecular weight could provide more active sites for the interaction between HA and iron minerals. Moreover, the carbon chain and aromatic nucleus in the high molecular weight HA fractions could keep the space structure of HA stable. • High pure lignite humic acid was fractionated successfully by ultrafiltration. • The differences of composition and structure of various HA fractions were investigated. • The structure proportion of HA was quantized by integral and PARAFAC method. • The smaller HA molecular had more abundant oxygen-bearing groups. • The larger HA molecular had more aromatic structures.

Impact of CeO2 nanoparticles on the aggregation kinetics and stability of polystyrene nanoplastics: Importance of surface functionalization and solution chemistry

The increasing application of plastics is accompanied by increasing concern over the stability and potential risk of nanoplastics. Heteroaggregation with metal-based nanoparticles (e.g., CeO2-NPs) is critical to the environmental mobility of nanoplastics, as they are likely to be jointly emitted to the aquatic environment. Here, time-resolved dynamic light scattering was employed to evaluate the influence of CeO2-NPs on the aggregation kinetics of differentially surface functionalized polystyrene nanoplastics (PS-NPs) in various water types. Natural organic matters and ionic strength were dominating factors influencing the heteroaggregation of PS-NPs and CeO2-NPs in surface waters. The critical coagulation concentrations of PS-NPs were dependent on their surface coatings, which decreased in the presence of CeO2-NPs due to electrostatic attraction and/or specific adsorption. Incubation of PS-NPs and CeO2-NPs under different pH confirmed the importance of electrostatic force in the aggregation of PS NPs. A relatively low humic acid (HA) concentration promoted the heteroaggregation of NH2-coated PS-NPs and CeO2-NPs because the introduction of a HA surface coating decreased the electrostatic hindrance. At high HA concentrations, the aggregation was inhibited by steric repulsion. The combined effects of high efficiency of double layer compression, bridging and complexation contributed to the high capacity of Ca2+ in destabilizing the particles. These findings demonstrate that the environmental behavior of nanoplastics is influenced by the presence of other non-plastic particles and improve our understanding of the interactions between PS-NPs and CeO2-NPs in complex and realistic aqueous environments.

Protaetia brevitarsis larvae can feed on and convert spent mushroom substrate from Auricularia auricula and Lentinula edodes cultivation

The edible mushroom industry produces massive amounts of spent mushroom substrate (SMS). Thus, there is an urgent need for high-value utilization technology to process the SMS, especially SMSs originating from woodchips. Protaetia brevitarsis larvae (PBL) can feed on various types of organic matter and can produce organic fertilizer and insect protein. In this study, we investigated the potential of PBL to utilize and convert SMSs from Auricularia auricula (SMS-AA) and Lentinula edodes (SMS-LE) cultivation. The results showed that the PBL were able to feed on SMS-AA and SMS-LE and form nutrient-enriched organic fertilizer with a low phytotoxicity and high humic acid content. Further analysis of the organic carbon dynamics suggested that PBL can efficiently digest and utilize lignin. This study demonstrates a new strategy for the utilization of SMSs originating from woodchips, and provides a new model for further investigations on the mechanism of lignin decomposition.