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.

The Promotion Effect of Low-Molecular Hydroxyl Compounds on the Nano-Photoelectrocatalytic Degradation of Fulvic Acid and Mechanism

A significant promotion effect of low-molecular hydroxyl compounds(LMHCs) was found in the nano-photoelectrocatalytic(NPEC) degradation of fulvic acid(FA),which is a typical kind of humic acid existing widely in natural water bodies,and its influence mechanism was proposed.A TiO_2 nanotube arrays(TNAs) material is served as the photoanode.Methanol,ethanediol,and glycerol were chosen as the representative of LMHCs in this study.The adsorption performance of organics on the surface of TNAs was investigated by using the instantaneous photocurrent value.The adsorption constants of FA,methanol,ethanediol,and glycerol were 43.44,19.32,7.00,and 1.30,respectively,which indicates that FA has the strongest adsorption property.The degradation performance of these organics and their mixture were observed in a thin-layer reactor.It shows that FA could hardly achieve exhausted mineralization alone,while LMHCs could be easily oxidized completely in the same condition.The degradation degree of FA,which is added LMHCs,improves significantly and the best promotion effect is achieved by glycerol.The promotion effect of LMHCs in the degradation of FA could be contributed to the formation of a tremendous amount of hydroxyl radicals in the NPEC process.The hydroxyl radicals could facilitate the complete degradation of both FA and its intermediate products.Among the chosen LMHCs,glycerol molecule which has three hydroxyls could generate the most hydroxyl radicals and contribute the best effective promotion.This work provides a new way to promote the NPEC degradation of FA and a direction to remove humus from polluted water.

Removal of Fulvic Acids from Aqueous Solutions via Surfactant Modified Zeolite

A surfactant modified zeolite（ SMZ）, i. e. , a zeolite modified by using hexadecyl trimethyl ammonium bromide （HDTMA） was used to remove fulvic acids（FA） from aqueous solution. The effects of the relevant parameters, such as the loading level of HDTMA, the contact time, the initial FA concentration, the pH, and the types of the metal carious and organics were examined. The results show that SMZ with an HDTMA loading-level of 120% of the external cation exchange capacity（ECEC） of zeolite exhibits the best performance. Although the removal of fulvic acids by SMZ occurs rapidly within the first 30 min of the contact time, a contact time of at least 4 h is required to attain the adsorption equilibrium. The removal capacity of FA by SMZ decreases with the increase of the initial FA concentration. The pH has an effect on the FA removal efficiency because it can influence the characteristics of the FA molecules. The removal of FA is considerably enhanced by Ca^2＋ or Mg^2＋ ions and is adversely affected by phenol or pentachlorophenol（PCP）. Under the optimum conditions, 98% of FA could be removed by SMZ. Furthermore, the desorption of FA and the regeneration of SMZ were studied. The results show that a 30% ethanol solution is sufficient for the regeneration of SMZ.

Fulvic acid degradation using nanoparticle TiO_2 in a submerged membrane photocatalysis reactor

The degradation of fulvic acid（FA） by nanoparticle TiO2 in a submerged membrane photocatalysis（SMPC） reactor was studied. In this reactor, photocatalytic oxidation and membrane separation co-occured. The continuous air supplier provided O2 for the photocatalytical reaction and mixed the solution through an airflow controller. The particle TiO2 could automatically settle due to gravity without particle agglomeration so it could be easily separated by microfiltration（MF） membrane. It was efficient to maintain high flux of membranes. The effects of operational parameters on the photocatalytic oxidation rate of FA were investigated. Results indicated that photocatalyst at 0.5 g/L and airflow at 0.06 m^3/h were the optimum condition for the removal of fulvic acid, the removal efficiency was higher in acid media than that in alkaline media. The effects of different filtration duration on permeate flux rate of MF with P25 powder and with nanoparticle TiO2 were compared. Experimental results indicated that the permeate flux rate of MF was improved and the membrane fouling phenomenon was reduced with the addition of nanoparticle TiO2 catalyst compared with conventional P25 powder. Therefore, this submerged membrane photocatalysis reactor can faciliate potential application of photocatalytic oxidation process in drinking water treatment.

Adsorption characterizations of fulvic acid fractions onto kaolinite

Fulvic acids extracted from a typical rice-production region near Taihu Lake of China were fractionated into three fractions including F4.8, F7.0 and F11.0 （eluted by pH 4.8 buffer, pH 7.0 buffer and pH 11.0 buffer, respectively）. Sorption of fulvic acid （FA） fractions onto kaolinite was studied by batch adsorption experiments, and characterizations of kaolinite before and after adsorption were investigated using scanning electron microscopy （SEM）. Adsorption isotherms of kaolinite for three FA fractions fit well with the Langrnuir adsorption model. The adsorption density of the three fractions was positively correlated with the ratio of the amount of the alkyl carbon to that of carboxyl and carbonyl carbon in FA fractions and followed an order of F11.0 〉 F7.0 〉 F4.8. Hydrophobic interaction was one of the control mechanisms for the sorption of FA fraction onto kaolinite. SEM images confirmed that compared to blank kaolinite samples, kaolinite samples coated by a FA fraction displayed an opener and more dispersed conformation resulting from the disruption of the floc structure in complex. Dispersion of kaolinite after adsorption was due to the repulsion between negatively charged FA-coated particles, which is closely related to the amount of FA fractions absorbed on kaolinite.

Compositional and Structural Difference of Fulvic Acid from Black Soil Applied with Different Organic Materials: Assessment After Three Years

Knowledge of different effects of various organic materials on soil humic substance is important for both environmental safety and sustainable agriculture.A pot experiment was conducted at Jilin Agricultural University,Jilin Province in northeast China to discover the influence of herb residue,animal excrement,woody residue,animal remnant on fulvic acid（FA） composition and structure using differential thermal analysis-thermogravimetric（DTA-TG）,fourier transform infrared spectroscopy（FTIR） and elemental analysis.DTA-TG showed the range of peak temperature in the first exothermic reaction increased following the trend： CK〉herb residue〉animal excrement〉woody residue=animal remnant,and the most weight loss was observed in animal excrement.Moreover,the second exothermic reaction of CK-and animal excrement-FA was presented as double peaks,the order of weight loss in that area was animal remnant〉CK〉woody residue〉animal excrement〉herb residue.According to FTIR,herb residue displayed higher adsorption intensity at 2 950,1 420,1 240 and 1 030 cm-1,animal excrement was in reverse.At the same time,herb residue-and animal excrement-FA had an absorption peak at 1 720 cm-1,while other organic materials didn＇t have this peak.As elemental analysis showed,FA isolated from various treatments was significantly distinct.It was clearly shown from our results that FA composition and structure in amended soils may be affected in different ways and at various extents on dependence of the nature and origin of amendment.

Application of Biochemical Fulvic Acid Potassium in Transplantation of Trees

[Objective]The paper was to clarify the application of biochemical fulvic acid potassium on the survival rate and growth of various trees transplanted in the process of landscaping.[Method]Two experimental treatments(i.e.decomposed organic fertilizer+biochemical fulvic acid potassium water soluble fertilizer,decomposed organic fertilizer+compound fertilizer)were designed to determine the changes in physical and chemical properties before and after soil treatment,and the survival rate,plant height and ground diameter of four different cultivated plants within one year,and the effects of applying biochemical fulvic acid potassium on cultivated plants were investigated.[Result]The soil organic matter,total nitrogen,alkali-hydrolyzable nitrogen,soil available phosphorus,soil available potassium and p H value in the soil treated with decomposed organic fertilizer+biochemical fulvic acid potassium soluble fertilizer,and decomposed organic fertilizer+compound fertilizer increased significantly,and the soil bulk density decreased obviously.The survival rates,plant heights and ground diameters of four different cultivated plants were significantly improved after application of decomposed organic fertilizer+biochemical fulvic acid potassium water soluble fertilizer,and decomposed organic fer-tilizer+compound fertilizer(P<0.05).[Conclusion]The application of biochemical fulvic acid potassium on cultivated plants effectively improved soil fertility,increased the utilization of nitrogen,phosphorus and potassium,improved the growth of plants,and promoted the growth of landscaping plants after transplantation.

The damage effects of oxy free radicals and fulvic acid on chondrocytes

The damage effects of oxy free radical and fulvic acid on cultivated chicken embryo chondrocytes were studied. The results show that the growrth of chondrocytes is inhibited and the morphology of the cells altered. The collagen synthesizing capability of the damaged cell changes somewhat. A noteworthy change of the type of collagen synthesized by the abnormal cells was observed by CMC-chromatography and amino acid analysis. The results indicated that the abnonml cells tend to synthesize type I instead of type II collagen, which is synthesized and secreted by the intact chondrocyte.

The oxidation damage of type II collagen by oxy free radicals and fulvic acid

The features of oxidative damage to type II collagen from pig cartilage, induced by · OH, O2- and fulvic acid from epidemic district of KBD, were studied in vitro. The results from amino acid analysis of the damaged collagen are characterized by a decrease in hydroxyproline and proline contents, and an increase in glutamic acid content. The change arc dependent on·OH and FA concentration. It is postulated that the FA or other toxic xenobiotics induce the generation of free radicals, which play the role of the trigger in KBD development.

Long-time Fulvic Acid Supplementation Modulates Hydroxylysyl Glycosylation of Collagen in Mice

In order to investigate the impact of fulvic acid (FA) on the hydroxylysyl glycosylation in collagen bio-synthesis, 40 NMRI mice were divided into two groups (n=20 in each group, consisting 10 females and 10 males). The animal was maintained for two generations by different diets: control group with normal water and food and study group with water containing 30mg/L FA and normal food. The second generation of the animal was slaughtered, and the biochemical parameters of collagen content and the degree of collagen hydroxylysyl glycosylation in skin, rib and tibia were detected by biochemical methods. The mean value of collagen in the study group was increased slightly, and no significant difference between study group and control group was found (P> 0.05), but the content of glucose-glactose-hydroxylysine (GGH) was significantly decreased in the study group in comparison with the control group (P<0.01). It was suggested that through the decrease of GGH 30 mg/L FA could inhibit the activity of galactosyl-hydroxylysylglucosyl-transferase and further disturb the post-translational modification of collagen intracellularly.

An Experimental Study on the Production of Fulvic Acid from Brown Coal Using N-Mn-TiO_2 as a Catalyst and H_2O_2 or HNO_3 as an Oxidizer

[Objective] The study aimed to extract fulvic acid from brown coal using N-Mn-TiO2 as a catalyst and H2O2 or HNO3 as an oxidizer. [Method] The effects of catalyst N-Mn-TiO2 on the yield and structure of fuMc acid were studied, and the content of functional groups in fulvic acid was analyzed qualitatively and quantitatively. [ Reselt] Two catalysts could improved the yield of fulvic acid, that is, catalyst 1 （N： Mn： 13 = 16： 0.001：1, roasting temperature was 400 ℃） and catalyst 2 （N： Mn： Ti = 16： 0.001：1, roasting temperature was 100 ℃） increased OFA yield by 10.69% and 32.17% and NFA by 8.61% and 7.49% respectively. After the addition of catalysts, the content of total acid radicals in OFA changed little, and carboxyi content increased slightly, but phenolic hydroxyl content decreased. When HNO3 was used as an oxidizer, the content of total acid radicals and phenolic hydroxyl in NFA decreased. In addition, the structure of OFA was different from that of NFA. [Condusion] The research could provide scientific references for the development and application of brown coal in future.

Determination of Formation Constants of Co^2＋,Ni^2＋,Cu^2＋and Zn^2＋ Complexes with Humic and Fulvic Acids by Potentionmetric Titration Method

The formation constants of Co^2+,Ni^2+,Cu^2+ and Zn^2+ complexes with humic acid(HA) and fulvic acid(FA) in red soil wrer determined by the potentiometric titration method.The constants as a function of composition of the complexation solutions were obtained by two graphical approaches respetively,The formation constants decreased with increasing concentration of metal in the solution,The results provide unambiguous evidence for the heterogeneity of the function groups of humic substances,the formation constants of FA were much smaller than those of HA,and the formation constants of Cu^2+ were much greater than those of Co^2+ ,Ni^2+ and Zn^2+,The potentiometric titration methon for determining formation constants are also discussed in the article.

Acid-base buffer effect of fulvic acid and barium fulvate from weathered coal

The acid-base buffer characteristics of fulvic acid (FA) and barium fulvate (BaFA)were analyzed. Each share of the sample or model agents (phthalic acid and salicylic acid)were separately mixed into a series of shares of dilute solutions of HCI or NaOH with a series of concentration. The original pH values of the solutions were arranged from 2 to 13.Final balanced pH of each share was measured. The pH changes show that FA and BaFApossess buffer ability, whereas the model agents do not. The tendency of balanced pHvalues was 5.4 for FA and 7.4 for BaFA, whereas the original pH was 4.0-8.5; balancedpH changed little. At room temperature, the maximum buffer capacities were as follows:18.11 mmol hydroxyl per gram FA, 11.25 mmol hydroxyl per gram BaFA, 1.19 mmol protonper gram FA, and 1.45 mmol proton per gram BaFA. Mathematics analysis shows thatlogarithm of buffer capacities of FA and BaFA is linearly dependent on original pH. Compared with BaFA and model agents, it is concluded that FA buffer capacity against hydroxylrelies not only on its acidic groups, BaFA buffer capacity against hydroxyl does not rely onits acidic groups, and FA buffer capacity against proton is not related with its carboxyl andphenolic hydroxyl group. The pH values of FA-water solutions with different concentrationsfrom 1 to 10 grams per liter were measured. Their pH values were slightly affected by itsconcentration. Thus, FA possesses a much stronger buffer ability against water dilutionthan common buffer agent. All the pH values of FA water solutions were very nearby 5.4,just the same as the balanced pH tendency for adding FA.

Degradation properties of fulvic acid and its microbially driven mechanism from a partial nitritation bioreactor through multi-spectral and bioinformatic analysis

This study employed multispectral techniques to evaluate fulvic acid(FA)compositional characteristic and elucidate its biodegradation mechanisms during partial nitritation(PN)process.Results showed that FA removal efficiency(FRE)decreased from 90.22 to 23.11%when FA concentrations in the reactor were increased from 0 to 162.30 mg/L,and that molecular size,degree of aromatization and humification of the effluent FA macromolecules all increased after treatment.Microbial population analysis indicated that the proliferation of the Comamonas,OLB12 and Thauera exhibit high FA utilization capacity in lower concentrations(<50.59 mg/L),promoting the degradation and removal of macromolecular FA.In addition,the sustained increase in external FA may decrease the abundance of above functional microorganisms,resulting in a rapid drop in FRE.Furthermore,from the genetic perspective,the elevated FA levels restricted carbohydrate(ko00620,ko00010 and ko00020)and nitrogen(HAO,AMO,NIR and NOR)metabolism-related pathways,thereby impeding FA removal and total nitrogen loss associated with N_(2)O emissions.

Metagenomic insights into responses of microbial population and key functional genes to fulvic acid during partial nitritation

The long-term impact of fulvic acid(FA)on partial nitritation(PN)systemwas initially examined in this study.The obtained results revealed that the FA lower than 50 mg/L had negligible effect on the nitrite accumulation rate(NAR nearly 100%)and ammonium removal rate(ARR 56.85%),while FA over 50 mg/L decreased ARR from 56.85%to 0.7%.Sludge characteristics analysis found that appropriate FA(<50 mg/L)exposure promoted the settling performance and granulation of PN sludge by removing Bacteroidetes and accumulating Chloroflexi.The analysis of metagenomics suggested that the presence of limited FA(0-50 mg/L)stimulated the generation of NADH,which favors the denitrification and nitrite reduction.The negative impact of FA on the PN system could be divided into two stages.Initially,limited FA(50-120 mg/L)was decomposed by Anaerolineae to stimulate the growth and propagation of heterotrophic bacteria(Thauera).Increasing heterotrophs competed with AOB(Nitrosomonas)for dissolved oxygen,causing AOB to be eliminated and ARR to declined.Subsequently,when FA dosage was over 120 mg/L,Anaerolineae were inhibited and heterotrophic bacteria reduced,resulting in the abundance of AOB recovered.Nevertheless,the ammonium transformation pathway was suppressed because genes amoABC and hao were obviously reduced,leading to the deterioration of reactor performance.Overall,these results provide theoretical guidance for the practical application of PN for the treatment of FA-containing sewage.

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.

Variation in humic and fulvic acids during thermal sludge treatment assessed by size fractionation, elementary analysis, and spectroscopic methods

Thermal pretreatment can be applied to sludge anaerobic digestion or dewatering. To analyze the variation in humic substances during thermal sludge treatment, sludge humic and fulvic acids were extracted before and after 30-min thermal treatment at 180℃, and then their contents, molecular weight distributions, elementary compositions, and spectral characteristics were compared. The results showed that the total contents of humic and fulvic acids in the sludge almost remained constant during thermal treatment, but 35% ofhumic and fulvic acids were dissolved from the sludge solids. Moreover, both humic and fulvic acids were partly decomposed and 32% of humic acids were converted to fulvic acids. The median value of the molecular weights of humic acids decreased from 81 to 41 kDa and that of fulvic acids decreased from 15 to 2 kDa. Besides the reduction in molecular size, the chemical structures of humic and fulvic acids also exhibited a slight change, i.e. some oxygen functional groups disappeared and aromatic structures increased after thermal sludge treatment.