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...

Study on the action and mechanism of humic acids in Kaschin-Beck disease

Humic acids, especially FA in fractions, contain more oxygen functional groups. In this experiment, on the basis of confirming the action of humic acids on KBD, what was studied is the biological effects of one of main oxygen functional groups, hydroxy group (-OH). The results indicate that inducing pathologic process of KBD, obviously decrease the GSH-Px activity and induce peroxidation membrane injury of tissue. The SOD activity increase in the tissues caused by oxygen functional groups showed that enhancing of free radical reaction should not be neglected.

Experimental Study on the Method of Extracting Humic Acids from Brown Coal Using Hydrogen Peroxide

[ Objective l The study aimed to discuss the optimal conditions of extracting humic acids from brown coal using hydrogen peroxide （H202）. [ Method] Fulvic acid （FA） was prepared through oxidizing the brown coal from Qujing City, Yunnan Province using H202, and humic acids were extracted from the original brown coal and its residues respectively, then the dominate constituents of humic acids were obtained by using pH grading method, finally their chemical composition of humid acids was characterized by Fourier transform infrared spectrometry and func- tional group content analysis. [Result] The mass ratio of the brown coal and oxidant affected the yield of FA most obviously, followed by oxidization temperature and duration, while oxidant concentration had no obvious effect. The optimum conditions were determined as follows： coal-oxidant ratio was 1 ： 0.60, oxidization temperature was 45 ℃, oxidization duration was 210 min, and the concentration of hydrogen peroxide was 20%. Under the conditions, the yield of FA was up to 20.40%. Analysis of component properties indicated that the content of carboxyl and total acidic groups in FA improved obviously under the optimum conditions, and the content of active functional groups in OHA was higher than that of HA, while the domi- nate constituents of OHA needed higher pH during precipitation compared with those of HA. [ Conclusion] The research could provide a new method to prepare good humic acids using brown coal,

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.

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.

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.

Study on Humic Acids of the Soil Applied with Corn Stalk by Spectroscopy Measurements

Spectroscopy measurements （Fourier transform infrared differential spectroscopy, Carbon-13 nuclear magnetic resonance spectrometry, Matrix-assisted laser resorption/ionization-time of flight mass spectrometry） were performed to study the humic acids of the soil applied with corn stalk. The results showed that after incorporation of corn stalks into the soil, the soil humic acid （HA） changed significantly in different stages. During first 60 days, new HAs were formed by polymerization and seems to be similar to that of initial HAs from composting corn stalk, some little molecular organic matters also reacted with soil HAs and turned into parts of soil HAs. After 60 days of the corn stalk residue incorporation, new HAs were formed by polymerization of decomposed lignin molecules, some methylenes transformed into methyls and methoxyls since the 90th day. Application of corn stalk led to the increase of aliphatic components in soil HAs, the decrease in aromatic components of soil HAs and the suppression in oxidation degree of soil HAs. The average molecular weight of soil HAs also declined because of application of corn stalk.

Removal of pharmaceutical in a biogenic/chemical manganese oxide system driven by manganese-oxidizing bacteria with humic acids as sole carbon source

Bioaugmented sand filtration has attracted considerable attention because it can effectively remove contaminants in drinking water without additional chemical reagent addition.In this study,a synthesized chemical manganese dioxide (MnO_(2)) -coated quartz sand(MnQS) and biogenic manganese oxide (BioMnOx) composite system was proposed to simultaneously remove typical pharmaceutical contaminants and Mn_(2)+.We demonstrated a manganese-oxidizing bacterium,Pseudomonas sp.QJX-1,could oxidize Mn_(2)+to generate BioMnOxusing humic acids (HA) as sole carbon source.The coaction of MnQS,QJX-1,and the generated BioMnOxin simultaneously removing caffeine and Mn_(2)+in the presence of HA was evaluated.We found a synergistic effect between them.MnQS and BioMnOxtogether significantly increased the caffeine removal efficiency from 32.8%(MnQS alone) and 21.5%(BioMnOxalone) to 61.2%.Meanwhile,Mn_(2)+leaked from MnQS was rapidly oxidized by QJX-1 to regenerate reactive BioMnOx,which was beneficial for continuous contaminant removal and system stability.Different degradation intermediates of caffeine oxidized by MnQS and BioMnOxwere detected by LC-QTOF-MS analysis,which implied that caffeine was oxidized by a different pathway.Overall,this work promotes the potential application of bioaugmented sand filtration in pharmaceutical removal in the presence of natural organic matter in drinking water.

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.

Evaluation of adsorption capacities of humic acids extracted from Algerian soil on polyaniline for application to remove pollutants such as Cd(Ⅱ), Zn(Ⅱ) and Ni(Ⅱ) and characterization with cavity microelectrode

The adsorption capacities of new humic acids isolated from Yakouren forest （YHA） and Sahara （Tamenrasset： THA） soils （Algeria） and commercial humic acid （PFHA） on polyaniline emeraldine base （PEB） were studied at pH 6.6. Also the adsorption of heavy metals such as Cd 2＋ , Zn 2＋ and Ni 2＋ on humic acid-polyaniline systems （HA-PEB） was investigated at the same conditions. HA-PEB compounds were characterized by scanning electron microscopy （SEM）, infrared spectrometry and cavity microelectrode. In addition, batch adsorption and cavity microelectrode were used in the adsorption study of Cd 2＋ , Zn 2＋ and Ni 2＋ on HA-PEB. To develop biocaptors of polluting metals using a cavity microelectrode modified by HA-PEB systems, the adsorption kinetic and adsorption capacity were investigated. The SEM analysis showed that the presence of humic acid affected the PEB surface and caused the formation of a granular morphology. The maximum adsorption capacities （q max ） of PFHA, THA and YHA determined by adsorption isotherms were 91.31, 132.1 and 151.0 mg/g, respectively. Batch adsorption results showed that q max of Cd 2＋ , Zn 2＋ and Ni 2＋ on HA-PEB followed the order： THA-PEB YHA-PEB PFHA-PEB. The voltammograms obtained with HA-PEB modified cavity microelectrode showed the appearance of new redox couples reflecting the adsorption of HA on PEB. Metal-humic acid-polyaniline voltammograms were characterized by appearance of oxidation-reduction couples or reduction wave corresponding to metal. Finally, the result may be exploited to develop a biocaptor based on the cavity microelectrode amended by THA-PEB and YHA-PEB.

Bioreduction of hexavalent chromium:Effect of compost-derived humic acids and hematite

Composting can enhance the nutrie nt ele ments cycling and reduce carbon dioxide production.However,little information is available regarding the application of compost for the remediation of the contaminated soil.In this study,we assess the response of the redox capacities(electron accepting capacities(EAC)and electron donating capacities(EDC))of compost-derived humic acids(HAs)to the bioreduction of hexavalent chromium(Cr(Ⅵ)),especially in presence of hematite.The result showed that the compost-derived HAs played an important role in the bioreduction of Cr(Ⅵ)in presence and absence of hematite under the anoxic,neutral(pH 7)and motionless conditions.Based on the pseudo-first order kinetic model,the rate constants of Cr(Ⅵ)reduction increased by 1.36-2.0 times when compost-derived HAs was added.The redox capacity originating from the polysaccharide structure of compost-derived HAs made them effective in the direct Cr(Ⅵ)reduction(without MR-1)at pH 7.Meanwhile,the reduction rates were inversely proportional to the composting treatment time.When iron mineral(Fe_(2)O_(3))and compost-derived HAs were both present,the rate constants of Cr(Ⅵ)reduction increased by 2.35-5.09,which were higher than the rate of Cr(Ⅵ)reduction in HA-only systems,indicating that the hematite played a crucial role in the bioreduction process of Cr(Ⅵ).EAC and quinonoid structures played a major role in enhancing the bioreduction of Cr(Ⅵ)when iron mineral and compost-derived HAs coexisted in the system.The results can extend the application fields of compost and will provide a new insight for the remediation of Cr(Ⅵ)-contaminated soil.

Comparative characterization of two natural humic acids in the Pearl River Basin, China and their environmental implications

Two humic acids （HAs） were isolated from contaminated river sediments present under comparative conditions in the Pearl River Basin, China. YFHA （the HA extracted at an open pyrite mining area in Yunfu） exhibited a lower absorption intensity for certain bands in the Fourier transform infrared spectra, a lower E 4 /E 6 value （the UV absorbances at 465 nm （E 4 ） and 665 nm （E 6 ））, a lower apparent molecular weight, a lower polarity and a lower oxygen functionality in comparison with GZHA （the HA isolated at an urban living area in Guangzhou）. All these differences indicated a higher degree of humification of YFHA than GZHA. Overall, the enrichment patterns of permanent heavy metals in the studied HAs were similar to those in corresponding sediments. In particular, YFHA exhibited high enrichment of trace element Tl, a characteristic concomitant from the mining of the pyrite minerals. The adsorption isotherms of two HAs for goethite and pyrolusite, two representative geological materials, conformed to the Langmuir equation. Based on the qualitative relationships between the Langmuir constants of the adsorption isotherms and the chemical characteristics of HAs, the main mechanism of HA adsorption on these materials was suggested to be hydrophobic interaction. This study highlighted the promising use of HA as a peculiar bio-indicator of uncommon trace metal contaminations. The HA adsorption mechanism on representative geological materials further provided a theoretical basis for the study on the unusual metal behavior in complex environmental settings.

Relating Cd2+binding by humic acids to molecular weight:A modeling and spectroscopic study

Molecular weight（Mw） is a fundamental property of humic acids（HAs）, which considerably affect the mobility and speciation of heavy metals in the environment. In this study, soil humic acid（HA） extracted from Jinyun Mountain, Chongqing was ultra-filtered into four fractions according to the molecular weight, and their properties were characterized.Complexation of cadmium was investigated by titration experiments. For the first time,Langmuir and non-ideal competitive adsorption-Donna（NICA-Donnan） models combined with fluorescence excitation-emission matrix（EEM） quenching were employed to elucidate the binding characteristics of individual Mw fractions of HA. The results showed that the concentration of acidic functional groups decreased with increasing Mw, especially the phenolic groups. The humification degree and aliphaticity increased with increasing Mw as indicated by elemental composition analysis and FT-IR spectra. The binding capacity of Cd2＋ to Mw fractions of HA followed the order UF1（〈 5 kDa） 〉 UF2（5–10 kDa） 〉 UF4（〉 30 kDa） 〉 UF3（10–30 kDa）. Moreover, the distribution of cadmium speciation indicated that the phenolic groups were responsible for the variations in binding of Cd2＋ among different Mw fractions. The results of fluorescence quenching illustrated that the binding capacity of Cd2＋ to Mw fractions was controlled by the content of functional groups, while the binding affinity was largely influenced by structural factors. The results provide a better understanding of the roles that different HA Mw fractions play in heavy metal binding,which has important implications in the control of heavy metal migration and bio-toxicity.

Effect of humic acids and sunlight on the cytotoxicity of engineered zinc oxide and titanium dioxide nanoparticles to a river bacterial assemblage

The effect of a terrestrial humic acid （HA） and Suwannee River HA on the cytotoxicity of engineered zinc oxide nanoparticles （ZnONPs） and titanium dioxide nanoparticles （TiO2NPs） to natural aquatic bacterial assemblages was measured with spread plate counting. The effect of HA （10 and 40 ppm） on the cytotoxicity of ZnONPs and TiO2NPs was tested factorially in the presence and absence of natural sunlight （light irradiation （LI））. The experiment was of full factorial, completely randomized design and the results were analyzed using the General Linear Model in SAS analytical software. The method of least squares means was used to separate the means or combinations of means. We determined the mechanism of toxicity via measurements of oxidative stress and metal ions. The toxicity of ZnONPs and TiO2NPs to natural aquatic bacterial assemblages appears to be concentration dependent. Moreover, the cytotoxicity of ZnONPs and TiO2NPs appeared to be affected by HA concentration, the presence of sunlight irradiation, and the dynamic multiple interactions among these factors. With respect to light versus darkness in the control group, the data indicate that bacterial viability was inhibited more in the light exposure than in the darkness exposure. The same was true in the HA treatment groups. With respect to terrestrial versus Suwanee River HA for a given nanoparticle, in light versus darkness, bacterial viability was more inhibited in the light treatment groups containing the terrestrial HA than in those containing Suwanee River HA. Differences in the extent of reactive oxygen species formation, adsorption/binding of ZnONPs/TiO2NPs by HA, and the levels of free metal ions were speculated to account for the observed cytotoxicity. TEM images indicate the attachment and binding of the tested nanoparticles to natural bacterial assemblages. Besides the individual parameter, significant effects on bacterial viability count were also observed in the following combined treatments： HA-ZnONPs, HA-LI, ZnONPs-LI, and HA-ZnONPs-LI. The main effects of all independent variables, plus interaction effects in all cases were significant with TiO2NPs.

Complex behaviour of trivalent rare earth elements by humic acids

The complexation behaviours of trivalent rare earth elements (La, Ce, Ho and Yb) by two types of humic acids were investigated under a specified set of conditions. Humic acids show quite different complexation capacities an conditional formation constants with the REEs. Apparently there are two types of binding sites in the functional groups of humic acid, in which the first binding sites have stronger ability than the second. Cerium shows the largest complexation capacities and highest formation constants among the four REEs with two humic acids, this anomaly may be relative to the distribution pattern of the REEs in seawater. The experimental results were comparable to the values of other metals reported and provided the basic data for environmental geochemistry of rare earth elements.

Effects of water quality on the coagulation performances of humic acids irradiated with UV light

The presence of humic acid in drinking water treatment has received significant attention in recent years because of its adverse effects on the removal of many pollutants in coagulation. In this paper, the effects of water quality including pH, turbidity, alkalinity, and hardness on the removal of humic acid were investigated in a UV light hybridized coagulation process. Our results suggested that UV light radiation could effectively improve the removal rate of humic acid in coagulation under both neutral and basic conditions, and the variations of the selected water quality parameters had little adverse effect on the function of UV light. After UV light radiation, the removal rate of the nitro-humic acid （NHA） increased from 20% to 60% in coagulation, and increased further to 75% and 85% for the raw waters with 10.0 NTU kaolin and 100mg.L-1 hardness, respectively. In addition to NHA, the removal rates of the humic acid extracted from peat coal （PHA） and the humic acid provided by Japan metals and chemicals company （JHA） in coagulation were also improved, both in the range of 80%-90% after undergoing UV light radiation. By changing the radiation location from prior to coagulation to the flocculation process, similar experimental results were obtained. The formation of positive charged sites after UV light radiation was considered to be the primary factor that led to an enhanced removal of the humic acid in coagulation.

Electrokinetic chemical characteristics of humic and dannic acids effecting on the natural water and its coagulation

Taking streaming current(SC)as the electrokinetic parameter,this paper demon- strated the electrokinetic chemical characteristics of humic and dannic acids(HA and DA)in sus- pensions including turbid water,coagulated water and HA or DA contained water.Accordingly, the studies were carried out for determining the relationship between streaming current and zeta po- tential ζ(expressed by eleetrophoretie mobility EM)in above water conditions.In addition,the mechanisms of HA effecting on streaming current within or after coagulant addition and the elec- trokinetic detection principles for HA or DA were also investigated on experiments and theoretical analysis.The results indicated that the change of SC like ζ presented meaningful information con- cerning the degree for destabilization of a particulate suspension,and HA or DA in water could re- markably decrease the effect of inorganic coagulant upon streaming current,which is in accordance with their influence on coagulation.

Humic acids derived from Leonardite to improve enzymatic activities and bioavailability of nutrients in a calcareous soil

Understanding the role of humic substances in soils is important for developing and utilizing organic fertilizers or soil amendments for sustainable agriculture.The objective of this study was to determine the effects of different fractions of humic acids derived from Leonardite on enzymatic activities and bioavailability of nutrients in a soil.The experiment was carried out by mixing different factions of humic acids with a soil and incubated for 70 d.The treatments included five factions of humic acids(HS1(low molecular weight),HS2(medium molecular weight)),HS3(large molecular weight,SED(sediment of fractions),HS(mixture of HS1,HS2,and HS3)),raw Leonardite(IM)and a control(no addition of humic acid).Experimental results showed that application of humic acids significantly improved acid and alkaline phosphatase activities,especially with HS1.Humic substances with high molecular weights significantly inhibit urease activity,and the optimal application rate was 600 kg/hm2 of humic substances with the high molecular weights.Concentrations of NH4+-N were decreased with increasing humus applications.All treatments(HSmix,HS1,HS2,HS3,IM,SED)did not affect the soil contents of Ca,although soil concentrations of K,P,Cu,Zn were increase significantly when small molecular weight humus(HS1)was applied.

On the applicability of the‘humic acids’nomenclature from natural ecosystems to engineering sciences

‘Humic acids(HA)’are the major constituents of natural organic matter(NOM)derived from the plant or biological residues by decomposition and synthesis in natural ecosystems.They have been defined as relatively high molecular weight aggregates of macromolecules associations with series of highly reactive functional compounds,and considered to be as irreplaceable roles(such as the impact on global carbon and nitrogen dynamics,atmosphere,living plants,chemically reactive and NOM structure stabilization)in natural ecosystems[1].

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.