Adsorption of lignite humic acid onto magnetite particle surface

Modified humic acid (MHA) binder based on lignite humic substances is a novel sort of promising organic binder for iron ore pellets.Humic acid (HA) is one of the main ingredients of MHA binder.Pure HA was firstly isolated from lignite and then adsorption of HA onto magnetite particle surface was investigated.The final results indicate that the adsorption of HA onto magnetite surface accords with Langmuir model well,and it is evidently influenced by the initial HA concentration and solution pH value.Adsorption depends on chemical interaction at pH values above the PZC (the pH where the Zeta potentials of minerals are zero) of magnetite,while electrostatic attraction and chemical interaction both contribute to the adsorption at pH values below the PZC.

Thermosensitive and Wound-Healing Gelatin-Alginate Biopolymer Hydrogels Modified with Humic Acids

The main goal of the article is the creation and study of thermosensitive and wound-healing gelatin-alginate bio-polymer hydrogels modified with humic acids.Their rheological properties,swelling and contraction behavior were experimentally investigated,elucidated using Fourier transform infrared spectroscopy and used to achieve the physiological melting point,which is necessary for successful drug delivery.It has been shown that in the gelatin-alginate-humic acid biopolymer hydrogels systems,it is possible to obtain a gel-sol transition temperature close to the physiological temperature of 37°C,which is important for drug delivery in the treatment of wounds.By changing the type and concentration of humic acids in the gelatin-alginate hydrogel,it turned out to be achiev-able to regulate the softening time of the gel on the human body in the range from 6 to 20 min,which provides the possibility of controlled prolonged delivery of drugs.Based on the study of the influence of calcium ions on the properties of humic acids and ion exchange,as well as the interaction of humic acids,sodium alginate and gelatin with the formation of tighter gel networks,approaches to regulate the rate of softening of hydrogels at physiological temperature and their swelling,which simulates the absorption of exudate,were proposed and implemented.In addition,low shrinkage of the hydrogel surface due to cross-linking of gelatin-alginate networks when modified with humic acids was experimentally confirmed,which is important for avoiding problems of wound contracture and contour deformations when using dressings for wound healing.Thus,the developed opti-mized innovative biopolymer hydrogels synergistically combine the outstanding properties of natural molecular polymers and humic acids and are promising for the creation of effective medicines for wound healing.

Effects of Three Humic Acid Foliar Fertilizers on Quality and Photosynthetic Characteristics of Hawthorn

[Objectives]To investigate the effects of three foliar fertilizers on photosynthetic characteristics,fruit quality and yield of hawthorn.[Methods]Taking hawthorn foliar fertilization as the reference,the photosynthetic rate,transpiration rate,intercellular CO 2 concentration,stomatal conductance and single fruit weight of hawthorn leaves were measured under different concentrations of foliar fertilizer.[Results]The results showed that the photosynthetic rate,transpiration rate and stomatal conductance of hawthorn leaves increased significantly,while the intercellular CO 2 concentration decreased.Specifically,the fish protein peptide foliar fertilizer performed best,with net photosynthetic rate and transpiration rate increased by 57.22%and 57.51%,respectively.All the three foliar fertilizers significantly reduced the intercellular CO 2 concentration.In addition,fertilization significantly increased the single fruit weight of hawthorn,and the effect of fermented fulvic acid foliar fertilizer was the most significant,with the highest growth rate of 68.49%.[Conclusions]Spraying foliar fertilizer significantly increased the content of Vc,titratable acid,anthocyanin and soluble solids of hawthorn fruit,among which fermented fulvic acid foliar fertilizer had the optimal effect.

Humic Acid Effects on Reducing Corn Leaf Burn Caused by Foliar Spray of Urea-Ammonium Nitrate at Different Humic Acid/Urea-Ammonium Nitrate Ratios

Technologies for reducing corn leaf burn caused by foliar spray of urea-ammonium nitrate (UAN) during the early growing season are limited. A field experiment was carried out to evaluate the effects of humic acid on corn leaf burn caused by foliar spray of undiluted UAN solution on corn canopy at Jackson, TN in 2018. Thirteen treatments of the mixtures of UAN and humic acid were evaluated at V6 of corn with different UAN application rates and different UAN/humic acid ratios. Leaf burn during 1 2, 3, 4, 5, 6, 7, and 14 days after UAN foliar spray significantly differed between with or without humic acid addition. The addition of humic acid to UAN significantly reduced leaf burn at each UAN application rate (15, 25, and 35 gal/acre). The reduction of leaf burn was enhanced as the humic acid/UAN ratio went up from 10% to 30%. Leaf burn due to foliar application of UAN became severer with higher UAN rates. The linear regression of leaf burn 14 days after application with humic acid/UAN ratio was highly significant and negative. However, the linear regression of leaf burn 14 days after application with the UAN application rate was highly significant and positive. In conclusion, adding humic acid to foliar-applied UAN is beneficial for reducing corn leaf burn during the early growing season.

Adsorption of Phthalic Acid Esters by Humic Acid and Its Research Progress

Humic acid is rich in highly electronegative oxygen-containing organic functional groups,so it has high reactivity and can adsorb phthalic acid ester(PAEs)in the environment to reduce the risk of environmental pollution from PAEs.In this paper,the extraction,characterization and adsorption models of humic acid were reviewed,and the research status of adsorption of PAEs by humic acid was further summarized.Based on these,the feasibility and observable application prospect of humic acid as a cheap adsorbent were analyzed.

Isotherm and kinetic studies on the adsorption of humic acid molecular size fractions onto clay minerals

Humic acid(HA)can adsorb onto mineral surfaces,modifying the physicochemical properties of the mineral.Therefore,understanding the sorption behavior of HA onto mineral surfaces is of particular interest,since the fate and transport of many organic and inorganic contaminants are highly correlated to HA adsorbed onto clay surfaces.Due to the extreme heterogeneity of HA,the extracted IHSS Leonardite humic acid(LHA)used in this work was fractionated using an ultrafiltration technique(UF)into different molecular size fractions(Fr1,>0.2μm;Fr2,0.2 pm-300,000 daltons;Fr3,300,000-50,000 daltons;Fr4,50,000-10,000 daltons;Fr5,10,000-1000 daltons).Equilibrium and the kinetics of LHA and fraction adsorption onto kaolinite and montmorillonite were investigated.The results demonstrated that the maximum adsorption capacity of LHA,Frl,Fr2,Fr3,Fr4,and Fr5 was 5.99,13.69,10.29,7.02,5.9&and 5.09 on kaolinite while it was 8.29,22.62,13.17,8.91,8.62,and 5.69 on montmorillonite,respectively.The adsorption equilibrium data showed that the adsorption behavior of LHA and its fractions could be described more practically by the Langmuir model than the Freundlich model.The rate of humic acid fraction adsorption onto clays increased with decreasing molecular size fraction and increasing carboxylic group content.Pseudo-first-and second-order models were used to assess the kinetic data and the rate constants.The results explained that LHA and its fractions adsorption on clay minerals conformed more to pseudosecondo rder.

Spectroscopic characteristics of two typical soil humic acids in China

Humic acid （HA） is known to be a complex organic compound with varying structural and functional characteristics. In this study, three-dimensional excitation emission matrix fluorescence spectroscopy （3DEEM）, ultraviolet-visible （UV-Vis） and Fourier-transform infrared （FT-IR） were applied to study the fluorescence characteristics and structure of two typical soil HAs in China. The effects of concentration of HA, pH and ionic strength on the fluorescence behaviors were investigated. The results indicate that ionic strength over the range from 0 to 0.05mol L^-1 NaNO3 did not affect the 3DEEM of HA. The concentration of HA and pH of the test solution had obvious effects on the 3DEEM. When the concentration of soil HA was lower than 10mg L^-1, HA has only one obvious fluorescence peak. However, there were several fluorescence peaks for HA in high concentration （≥50mg L^-1）, and its Ex/Em maximum wavelength shifted towards longer wavelength with increasing the concentration of HA. The fluorescence intensity of HA enhanced with the increase of pH, and achieved maximum at pH 10. The effect of pH on the fluorescence intensity of black soil HA （BHA） was the severest and a polycondensation of BHA existed with the change of pH. At the same condition, the fluorescence intensity of red soil HA （RHA） was stronger than that of BHA. At the excitation wavelength of 340nm, the maximum emission peak positions of RHA and BHA were 474 and 504nm at pH 6.0, and their fluorescence quantum yields （QY） were 2.1-2.5% and 1.5-1.9%, respectively. Based on the maximum emission peak positions and fluorescence quantum yield, RHA and BHA can be distinguished.

Effect of temperature on the sorption and desorption of perfluorooctane sulfonate on humic acid

Sorption and desorption of perfluorooctane sulfonate （PFOS） on humic acid at different temperatures were studied. It was found that the sorption process could be modeled with power kinetic equation very well, suggesting that diflusion predominated the sorption of PFOS on the humic acid. The sorption capacity was doubled when the temperature increased from 5 to 35°C, and thermodynamics parameters △G0 was calculated to be –7.11 to –5.04 kJ/mol, △H0 was 14.2 kJ/mol, and △S 0 was 69.5 J/（mol·K）, indicating that the sorption was a spontaneous, endothermic, and entropy driven process. Desorption hysteresis occurred at all studied temperatures which suggested that humic acid may be an important sink of PFOS in the environment.

Characterization of humic acids extracted from the sediments of the various rivers and lakes in China

The humic acids (HAs) isolated from the sediments of the various rivers,lakes,and reservoirs in China were studied using elemental analyzer,fourier transform infrared (FT-IR),and CP/MAS 13C nuclear magnetic resonance (NMR) spectroscopy.The results showed that the HAs were characterized by some common chemical and physicochemical properties,but they also pose some differences in the C-containing functional groups.The C/N,C/H,O/C,and O/H ratios differ widely for the various HAs,showing that the elemental comp...

Adsorption characteristics of humic acid-immobilized amine modified polyacrylamide/bentonite composite for cationic dyes in aqueous solutions

Humic acid-immobilized amine modified polyacrylamide/bentonite composite （HA-Am-PAA-B） was prepared and used as an adsorbent for the adsorption of cationic dyes （Malachite Green （MG）, Methylene Blue （MB） and Crystal Violet （CV）） from aqueous solutions. The polyacrylamide/bentonite composite （PAA-B） was prepared by intercalative polymerization of acrylamide with Nabentonite in the presence of N,N＇-methylenebisacrylamide as a crosslinking agent and hexamethylenediammine as propagater. PAA-B was subsequently treated with ethylenediammine to increase its loading capacity for HA. The surface characterizations of the adsorbent were investigated. The adsorbent behaved like a cation exchanger and more than 99.0% removal of dyes was detected at pH range 6.0-8.0. The capacity of HA-Am-PAA-B was found to decrease in the following order： MG〉MB〉CV. The kinetic and isotherm data were interpreted by pseudo-second order rate equation and Freundlich isotherm model, respectively. Experiments were carried out using binary solute systems to assess the competitive adsorption phenomenon. The experimental isotherm data for each binary solute combination of MG, MB and CV were analyzed using Sheindrof-Rebhun-Sheintuch （SRS） （multicomponent Freundlich type） equation.

Extraction and Characterization of Humic Acids and Humin Fractions from a Black Soil of China

Twenty-three progressive extractions were performed to study individual humic acids (HAs) and humin fractions from a typical black soil (Mollisol) in Heilongjiang Province, China using elemental analysis and spectroscopic techniques. After 23 HA extractions the residue was separated into high and low organic carbon humin fractions. HA yield was the highest for the first extraction and then gradually decreased with further extractions. Organic carbon (OC) of the humin fractions accounted for 58% of total OC …

Effects of fulvic acid and humic acid on aluminum speciation in drinking water

This article focused on the influences of fulvic acid and humic acid on aluminum speciation in drinking water. Factors including the concentration of residual chlorine and pH value had been concerned. Aluminum species investigated in the experiments included inorganic mononuclear, organic mononuclear, mononuclear, polymer, soluble, and suspended forms. It was found that the effects of fulvic acid and humic acid on aluminum speciation depended mainly on their molecular weight. Fulvic acid with molecular weight less than 5000 Dalton had little influence on aluminum speciation; while fulvic acid with molecular weight larger than 5000 Dalton and humic acid would increase the concentration of soluble aluminum significantly even at concentration below 0.5 mg/L （calculated as TOC）. Aluminum species, in the present of fulvic acid with molecular weight larger than 5000 Dalton and humic acid, were more stable than that in the present of fluvic acid with molecular mass less than 5000 Dalton, and varied little with reaction time. Within pH range 6.5-7.5, soluble aluminum increased notably in water with organic matter. As the concentration of residual chlorine increased, the effects of fulvic acid and humic acid became weak. The reactions between humic acid, fulvic acid with large molecular weight, and aluminum were considered to be a multi-dentate coordination process. With the consideration of aluminum bioavailability, reducing the concentration of fulvic acid and humic acid and keeping the pH value among 6.5-7.5 were recommended during drinking water treatment.

Ultrafiltration with in-line coagulation for the removal of natural humic acid and membrane fouling mechanism

Experimental and theoretical analysis were made on the natural humic acid removal and the membrane fouling of ultrafiltration （UF） with in-line coagulation. The results showed dissolved organic carbon （DOC） and UV254 removals by the UF with in-line coagulation at pH 7 were increased from 28% to 53% and 40% to 78% in comparison with direct UF treatment respectively. At the same time, the analysis of high performance liquid chromatography showed that UF with coagulation had significant improvement of removal of humic acid with molecular weights less than 6000 Da in particular. Compared to direct UF, the in-line coagulation UF also kept more constant permeate flux and very slight increase oftransmembrane pressure during a filtration circle. Two typical membrane fouling models were used by inducing two coefficients Kc and Kp corresponding to cake filtration model and pore narrowing model respectively. It was found that membrane fouling by pore-narrowing effect was effectively alleviated and that by cake-filtration was much decreased by in-line coagulation. Under the condition of coagulation prior to ultrafiltration at pH 7, the cake layer formed on the membrane surface became thicker, but the membrane filtration resistance was lower than that at pH 5 with the extension of operation time.

Photo-induced transformations of Hg(Ⅱ) species in the presence of Nitzschia hantzschiana,ferric ion,and humic acid

Effects of algae Nitzschia hantzschiana, Fe（Ⅲ） ions, humic acid, and pH on the photochemical reduction of Hg（Ⅱ） using the irradiation of metal halide lamps （λ〉 365 nm, 250 W） were investigated. The photoreduction rate of Hg（Ⅱ） was found to increase with increasing concentrations of algae, Fe（Ⅲ） ions, and humic acid. Alteration of pH value affected the photoreduction of Hg（Ⅱ） in aqueous solution with or without algae. The photoreduction rate of Hg（Ⅱ） decreased with increasing initial Hg（Ⅱ） concentration in aqueous solution in the presence of algae. The photochemical kinetics of initial Hg（Ⅱ） and algae concentrations on the photoreduction of Hg（Ⅱ） were studied at pH 7.0. The study on the total Hg mass balance in terms of photochemical process revealed that more than 42% of Hg（Ⅱ） from the algal suspension was reduced to volatile metallic Hg under the conditions investigated.

Study on the influence of humic acid of different molecular weight on basic ion exchange resin's adsorption capacity

In this paper, humic acid （HA） was ultra-filtered into different molecular weight sections and was characterized by multielement analysis, UV254/TOC, FT-IR and three-dimensional fluorescence spectrometric. Since humic acids of different molecular weights have different hydrophilic and molecular size, the maximum adsorption capacity of basic ion exchange resins appears on the humic acid whose molecular weight ranges from 6000 to 10,000 Da.

Kinetics study of aqueous sorption of phenanthrene to humic acids and sediments

The sorption behavior was determined for a model polycyclic aromatic hydrocarbon(PAH), i.e., phenanthrene(PHN), from water to three humic acids(HAs) and three sediments in different reacting time. The chemical compositions of HA samples were measured using cross polarization magic angle spinning carbon 13(CPMAS 13 C NMR along with elemental analysis. The dissolved humic substances dissociating from solid HAs and sediments were characterized by 1 H NMR. The experiments indicated that the sorption modes and mechanisms of natural sorbents for PHN varied significantly between short(<7 d) and long contact time and the reaction time should be taken into consideration in studying the overall sorption process. The sorption capacity( K ′ f) and exponent( n ) might be relative to the properties of dissolved humic materials in initial stage but the solid aromatic organic matter after long time reaction. According to the experiments performed in this investigation and the previous researches, a conceptive sorption model was established.

Adsorption of Cu(Ⅱ) on humic acids derived from different organic materials

The adsorption of Cu（Ⅱ） from aqueous solution onto humic acid （HA） which was isolated from cattle manure （CHA）, peat （PHA）, and leaf litter （LHA） as a function of contact time, pH, ion strength, and initial concentration was studied using the batch method. X-ray absorption spectroscopy （XAS） was used to examine the coordination environment of the Cu（ll） adsorbed by HA at a molecular level. Moreover, the chemical compositions of the isolated HA were characterized by elemental analysis and solid-state 13C nuclear magnetic resonance spectroscopy （NMR）. The kinetic data showed that the adsorption equilibrium can be achieved within 8 h. The adsorption kinetics followed the pseudo-second-order equation. The adsorption isotherms could be well fitted by the Langmuir model, and the maximum adsorption capacities of Cu（ll） on CHA, PHA, and LHA were 229.4,210.4, and 197.7 mg g-1, respectively. The adsorption of Cu（Ⅱ） on HA increased with the increase in pH from 2 to 7, and maintained a high level at pH〉7. The adsorption of Cu（Ⅱ） was also strongly influenced by the low ionic strength of 0.01 to 0.2 mol L-1 NaNO3, but was weakly influenced by high ionic strength of 0.4 to 1 mol L-1 NaNO3. The Cu（Ⅱ） adsorption on HA may be mainly attributed to ion exchange and surface complexation. XAS results revealed that the binding site and oxidation state of Cu adsorbed on HA surface did not change at the initial Cu（Ⅱ） concentrations of 15 to 40 mg L 1. For all the Cu（Ⅱ） adsorption samples, each Cu atom was surrounded by 40/N atoms at a bond distance of 1.95 A in the first coordination shell. The presence of the higher Cu coordination shells proved that Cu（Ⅱ） was adsorbed via an inner-sphere covalent bond onto the HA surface. Among the three HA samples, the adsorption capacity and affinity of CHA for Cu（Ⅱ） was the greatest, followed by that of PHA and LHA. All the three HA samples exhibited similar types of elemental and functional groups, but different contents of elemental and functional groups. CHA contained larger proportions of methoxyl C, phenolic C and carbonyl C, and smaller proportions of alkyl C and carbohydrate C than PHA and LHA. The structural differences of the three HA samples are responsible for their distinct adsorption capacity and affinity toward Cu（Ⅱ）. These results are important to achieve better understanding of the behavior of Cu（Ⅱ） in soil and water bodies in the presence of organic materials.

Study on correlation between humic acid and selenium in Kaschin-Beck disease areas

The relationship between humic acid and selenium content was studied in this research. The results of calculation showed that there is more humic acid and less selenium in Kaschin-Beck disease areas in China. Fulvic acid in soil could increase selenium level in plants. The chemical bonding between humic acid and selenium was observed with an I.R. spectroscope. It was remarkable for the changes of absorption peak and frequency in 1100-1000 cm-1, 900-700 cm-1.

Effects of methyl-CD and humic acid on hydrolytic degradation of the herbicide diclofop-methyl

Hydrolytic degradation of the herbicide diclofop methyl was investigated in the multi pH deionized water, natural aquatic systems and soil suspensions. Resulting data indicated that the herbicide was stable in the acidic and nearly neutral solutions for at least 15 d. The herbicide diclofop methyl rapidly dissipated in the natural aquatic systems and soil suspensions with half lives less than 4 d. Methyl CD(partially methylated β cyclodextrin) improved its hydrolytic degradation in the pH 8 deionized water and natural aquatic systems while humic acid inhibited its hydrolytic degradation at the same conditions. But dissolved organic matter in the natural aquatic systems and soil suspensions increased its hydrolysis. Two catalysis mechanisms were introduced to describe the effects of cyclodextrin and organic matter on its hydrolytic metabolism. Though inorganic ions maybe improved its hydrolysis reaction in the natural aquatic systems, Fe 2+ and Cu 2+ did not form complexes with the herbicide and had poor influences on its hydrolytic degradation whether cyclodextrin was added or not.

Characteristics of isothermal adsorption and desorption of aluminum ion to/from humic acids

The adsorption and desorption characteristics of Al^3＋ to/from humic acids at different pH, ionic strength, and temperature were studied by the C-25 glucosan-gel chromatography method. The results showed that the maximum adsorption amount （Qmax） and adsorption constant （k） increased, whereas, the absolute value of standard thermodynamic molar free energy change （ΔGm^0） decreased with the increase of pH at constant ionic strength and temperature. With ionic strength increasing from 0 to 0.15 mol/L, Qmax, and k increased and the absolute value of ΔGm^0 decreased at constant pH and temperature. High temperature was unfavorable for the adsorption reaction, as indicated by the dramatic decrease of Qmax and the absolute value of ΔGm^0 with an increase in temperature. The standard thermodynamic molar free energy change （ΔGm^0） and the standard thermodynamic enthalpy change （ΔHm^0） of the adsorption reaction were both negative, suggesting that adsorption reaction was spontaneous and exothermic. The desorption rate of HA-Al^3＋ complex accelerated with the decrease of pH, and a significant linear relationship could be obtained between pH and the desorption rates of Al^3＋ from humic acids. These results demonstrated that the Al^3＋ adsorption reaction was a ＂biphase＂ reaction, and adsorption occurred at both the interior and exterior adsorption sites of humic acids.