The contribution of alkali soluble (humic acid-like) and unhydrolyzed-alkali soluble (core-humic acid-like) fractions extracted from maize plant to the formation of soil humic acid

Alkali soluble (humic acid-like material) (HA-like) (yield of 132 gkgdm(-1)) and the unhydrolized-alkali soluble (core-humic acid-like material) (core-HA-like) (yield of 33.4 gkgdm(-1)) fractions were extracted from maize plants and characterized by C and N determinations, DRIFT, and 1H and 13C-NMR spectroscopy. Fresh plants were subsequently incubated for 6 months in an artificial mineral soil, and the HA-like and core-HA-like trends were monitored quantitatively (C fraction content) and qualitatively (spectroscopic approach) in order to study their contribution to the formation of soil humic acid. During incubation the HAC-like partially degraded (loss of 320 gkgHAC(-1)) and partially formed new fulvic-like acids (160 gkgHAC(-1)). On the contrary, the stable fraction of HAC, the core-HAC-like, was maintained (loss of 153 kgcore-HAC(-1)), representing, after incubation, 846 gkg(-1) of the initial core-HAC-like content. The core-HA-like fraction is composed of lignin residues, polysaccharides, lipids and proteins, probably structured into a well-defined network, i.e. the plant cell wall.     

Binding of Pb(II) in the system humic acid/goethite at acidic pH

The study of Pb(II) binding to the system humic acid/goethite in acidic medium is reported in the present paper. From a macroscopic point of view, we have constructed the experimental sorption isotherms (using atomic absorption spectroscopy) and compared them with the prediction of the additivity rule. It is found that this system presents positive deviations, that is, the amount sorbed is about an order of magnitude higher than predicted. Apart from this, microscopic and structural aspects have also been studied using in situ and ex situ infrared spectroscopy. These results suggest that the presence of Pb(II) increases the amount of humic acid bound to the oxide. It is proposed that proton displacement due to the interaction between humic substances and the oxide, along with the formation of ternary complexes with the Pb(II) cation bridging the oxide and the humic substances (Type A complexes), cause the deviation from additivity.     

Binding of Pb(II) in the system humic acid/goethite at acidic pH

The study of Pb(II) binding to the system humic acid/goethite in acidic medium is reported in the present paper. From a macroscopic point of view, we have constructed the experimental sorption isotherms (using atomic absorption spectroscopy) and compared them with the prediction of the additivity rule. It is found that this system presents positive deviations, that is, the amount sorbed is about an order of magnitude higher than predicted. Apart from this, microscopic and structural aspects have also been studied using in situ and ex situ infrared spectroscopy. These results suggest that the presence of Pb(II) increases the amount of humic acid bound to the oxide. It is proposed that proton displacement due to the interaction between humic substances and the oxide, along with the formation of ternary complexes with the Pb(II) cation bridging the oxide and the humic substances (Type A complexes), cause the deviation from additivity.     

Removal of Cr(VI) and humic acid by using TiO2 photocatalysis

The removal efficiencies of Cr(VI) and HA, using a TiO(2)-mediated photocatalytic process, were investigated with variations in the pH, TiO(2) dosage and Cr(VI)/HA ratio. During the photocatalytic reaction, the total removal of Cr(VI) occurred through adsorption onto TiO(2), as well as its reduction to Cr(III). However, oxidation and adsorption were identified as important removal processes for the treatment of HA. Due to the anionic type adsorption onto TiO(2) and its acid-catalyzed photocatalytic reduction, the removal of Cr(VI) decreased with increasing pH, while that of HA increased with increasing pH. The TiO(2) dosage was also an important parameter for the removal of Cr(VI). As the TiO(2) dosage was increased to 2.5 g l(-1), the removal of Cr(VI) was continuously enhanced, but decreased at dosages above 3 g l(-1) due to the increased blockage of the incident UV light used for the photocatalytic reaction. The removal of Cr(VI) was greatly enhanced when the system contained both HA and Cr(VI) compared to Cr(VI) alone. Also, the removal of HA was greatly enhanced when the system contained both HA and Cr(VI) compared to HA alone. The removal of Cr(VI) was continuously enhanced as the HA concentration gradually increased; however, no further increase was observed above 20 mg l(-1) HA due to the increased absorption of the UV light. This result supports that the photocatalytic reaction, with illuminated TiO(2), could be applied to more effectively treat wastewater containing both Cr(VI) and HA than that containing a single species only.     

Photocatalytic and photoelectrocatalytic humic acid removal and selectivity of TiO(2) coated photoanode

In this study, photocatalytic (PC) and photoelectrocatalytic (PEC) treatment methods were comparatively investigated as a possible means of removing humic acid (HA) following absorbance at 254nm (UV(254)) and total organic carbon (TOC) analysis. The enhanced HA degradation rates were obtained in the PEC system over the conventional PC process under acidic, neutral and alkaline conditions. Preliminary and binary experiments were performed to determine the selectivity of the photoanode in terms of HA and chloride oxidation. TOC, chlorine and photocurrent parameters proved that HA was selectively removed before chlorine generation. The inhibitory effect of carbonate ions on the performance of photoanode was also studied under different pH values.     

Simultaneous extraction of Cr(VI) and Cu(II) from humic acid with new synthesized EDTA derivatives

Soil washing is one of the few permanent treatment alternatives for removing metal contaminants. Ethylenediaminetetraacetic acid and its salts (EDTA) is very effective at removing cationic metals and has been utilized globally. However it is ineffective for anionic metal contaminants or metals bound to soil organic matter. The simultaneous removal of cationic and anionic metal contaminants by soil washing is difficult due to differences in their properties. The present study evaluated the potential of a washing process using two synthesized EDTA-derivatives, C₆HEDTA (2,2′-((2-((carboxymethyl)(2-(hexanoyloxy)ethyl)amino)ethyl)azanediyl)diacetic acid) and C₁₂HEDTA (2,2′-((2-((carboxymethyl) (2-(dodecanoyloxy)ethyl)amino)ethyl)azanediyl)diacetic acid), which consist of a hydrophilic polycarboxylic moiety and a hydrophobic moiety with a monoalkyl ester group. A series of equilibrium batch experiments at room temperature were conducted to investigate the efficacy of C₆HEDTA and C₁₂HEDTA as extractants for both oxyanion Cr(VI) and cationic Cu(II). Results showed that either C₆HEDTA or C₁₂HEDTA can extract both Cr(VI) and Cu(II) from humic acid simultaneously. However, C₆HEDTA was less effective for Cr(VI) probably because it has no surface activities to increase solubility of humic acid, like C₁₂HEDTA. Extraction of Cr(VI) was mainly attributed to the decreased surface tension and enhanced solubility of organic matter. Extraction of Cu(II) was attributed to both the Cu(II) chelation and enhanced solubility of humic acid. It was demonstrated that the hydrophilic polycarboxylic moiety of C₁₂HEDTA chelates cations while the monoalkyl ester group produces surface active properties that enhance the solubility of humic acid.     

Complexation of the antibiotic tetracycline with humic acid

The effect of solution chemistry and sorbate-to-sorbent ratio on the interaction of the antibiotic tetracycline with Elliott soil humic acid (ESHA) was investigated using equilibrium dialysis and FITEQL modeling. Tetracycline speciation strongly influenced its sorption to ESHA. Sorption was strongly pH-dependent with a maximum around pH 4.3, and competition with H+ and electrolyte cation (Na+) was evident. The pH-dependent trend was consistent with complexation between the cationic/zwitterionic tetracycline species and deprotonated sites in ESHA (mainly carboxylic functional groups). Modification of ESHA by Ca2+ addition increased tetracycline sorption suggesting that ternary complex formation (ESHA-metal-tetracycline) may be important at higher concentrations of multivalent metal cations. The macroscopic data (pH-envelope and sorption isotherms) were successfully modeled using a discrete logK function with the FITEQL 4.0 chemical equilibrium program indicating that ESHA-tetracycline interaction could be reasonably represented as complex formation of a monoacid with discrete sites in humic acid. Sorption-desorption hysteresis was observed; both sorption and desorption isotherms were well described by the Freundlich equation.     

Adsorption of arsenic (V) on kaolinite and on kaolinite-humic acid complexes. Role of humic acid nitrogen groups

In order to investigate the influence of organic matter on arsenic retention, we used batch experiments at pH 7 to determine the adsorption of As(V) on three different solids: a crude, purified, Ca-exchanged kaolinite and two kaolinites coated with humic acids (HAs) having different nitrogen contents. We first examined the adsorption of each HA onto kaolinite, and then used the HA-kaolinite complexes to study As(V) adsorption. The results clearly show an influence of the HA coating on As adsorption. For example, with low initial As concentrations the solid/liquid partition coefficient (R(d)) for both HA complexes is greater than that for the crude kaolinite. We found that increasing the initial As concentrations decreased the R(d) values of the HA-coated kaolinites until finally they were the same as the crude kaolinite R(d) values. This suggests that adsorption occurs first on the HA sites and then, once the HA sites are saturated, on the remaining kaolinite sites. We also noted that the more reactive HA-kaolinite complex was the one with the highest N/C ratio. Comparing the amount of amine groups in the HA-kaolinite complexes with the total amount of adsorbed As indicates that the HA amine groups, due to their positive charge at pH 7, play a key role in the adsorption of As onto organic matter.     

Reduction of silver solubility by humic acid and thiol ligands during acanthite (beta-Ag2S) dissolution

Precipitation of highly insoluble metal sulfide minerals like acanthite (beta-Ag2S) or red cinnabar (HgS) is in principle an effective means to reduce metal availability and toxicity in contaminated soils. Unfortunately, experiments have shown that red cinnabar may be solubilized in the presence of dissolved organic matter or thiol ligands. To determine whether the same applies to acanthite, a laboratory synthesized beta-Ag2S mineral was incubated for up to 3 weeks in the presence of KNO3, dissolved humic acids, cysteine, methionine and thiosulfate. XPS analysis identified Ag2O (52%), Ag2SO4 (8%) and Ag2S (40%) on the particle surfaces. Ag was released into solution in the presence of KNO3 and methionine, presumably from mixed-oxidation surface layers. Contrary to earlier results with cinnabar, however, humic acids reduced Ag concentrations in solution by about 75%, and cysteine and thiosulfate, each containing a free -SH functional group, almost completely suppressed Ag release into solution.     

Photochemical degradation of methylparathion in the presence of humic acid

Photochemical degradation of methylparathion (O,O,-dimethyl O-4 nitrophenylphosphorothioate) in the presence of humic acid between pH 2 and 7 was monitored by differential pulse polarography. Humic acid was not electro-active under the experimental conditions used in this study. Only the pesticide and its main degradation product at pH 2 exhibited polarographic signals. Photolysis of methylparathion in acid media was sensitized by humic acid since the pesticide did not degrade in the absence of this compound. Methylparathion degradation in the presence of humic acid was observed at each of the studied pHs. The reaction was first-order with rate constant values ranging from 2 x 10(-3) to 6.3 x 10(-3) min(-1).     

Photochemical degradation of methylparathion in the presence of humic acid

Photochemical degradation of methylparathion (O,O,-dimethyl O-4 nitrophenylphosphorothioate) in the presence of humic acid between pH 2 and 7 was monitored by differential pulse polarography. Humic acid was not electro-active under the experimental conditions used in this study. Only the pesticide and its main degradation product at pH 2 exhibited polarographic signals. Photolysis of methylparathion in acid media was sensitized by humic acid since the pesticide did not degrade in the absence of this compound. Methylparathion degradation in the presence of humic acid was observed at each of the studied pHs. The reaction was first-order with rate constant values ranging from 2 × 10^?3 to 6.3 × 10^?3 min^?1.     

Influences of redox transformation, metal complexation and aggregation of fulvic acid and humic acid on Cr(VI) and As(V) removal by zero-valent iron

This study investigated the removal kinetics and mechanisms of Cr(VI) and As(V) by Fe(0) in the presence of fulvic acid (FA) and humic acid (HA) by means of batch experiments. The focus was on the involvements of FA and HA in redox reactions, metal complexation, and iron corrosion product aggregation in the removal of Cr(VI) and As(V) removal by Fe(0). Synthetic groundwater was used as the background electrolyte to simulate typical groundwater. The results showed faster Cr(VI) removal in the presence of HA compared to FA. Fluorescence spectroscopy revealed that no redox reaction occurred in the FA and HA. The results of the speciation modeling indicate that the free Fe(II) concentration was higher in the presence of HA, resulting in a higher removal rate of Cr(VI). However, the removal of As(V) was inhibited in the HA solution. Speciation modeling showed that the concentration of dissolved metal-natural organic matter (metal-NOM) complexes significantly affected the aggregation of the iron corrosion products which in turn affected the removal of As(V). The aggregation was found to be induced by gel-bridging of metal-NOM with the iron corrosion products. The effects of metal-NOM on the aggregation of the iron corrosion products were further confirmed by TEM studies. Larger sizes of iron corrosion products were formed in the FA solution compared to HA solution. This study can shed light on understanding the relationships between the properties of NOM (especially the content of metal-binding sites) and the removal of Cr(VI) and As(V) by Fe(0).     

腐植酸对多环芳烃在污染土壤中淋出及截留分解的效果研究

多环芳烃是固废拆解地一类污染较严重的有毒有机物质,用腐植酸作表面活性剂淋洗污染土壤起到较好的增溶及截留分解污染物的作用,达到修复污染土壤的目的。实验结果表明,随着腐植酸加入量的增加,菲、萘、荧蒽、芘和∑PAHs的淋出量显著提高,在污染红壤中最大淋出率分别为52.9%、70.1%、30.5%、46.1%和42.8%,在污染水稻土中最大淋出率分别为51.8%、67.3%、35.0%、38.3%和35.5%,同时多环芳烃的截留分解率也相对较高,而污染红壤和水稻土的总修复率分别达到56.3%和49.8%。     

一维饱和多孔介质中胡敏酸的运移研究

研究了胡敏酸在不同多孔介质中的运移特征.结果表明:(1)CXTFIT.2.1软件对多孔介质中胡敏酸运移的拟合效果随多孔介质不同而有较大的差异,其对石英砂和河沙中胡敏酸的运移过程拟合较好,对3种土壤(风沙土、黄绵土和黑垆土)中胡敏酸的运移过程拟合较差.(2)胡敏酸溶液在多孔介质中的运移行为与不同多孔介质有关,在石英砂和河沙中运移迅速,而在土壤中运移缓慢;胡敏酸的快速运移对应较低的阻滞因子和吸附系数,而缓慢运移对应较高的阻滞因子和吸附系数.对于石英砂和河沙,胡敏酸的运移在石英砂中较快,在河沙中较慢;对于3种土壤(风沙土、黄绵土和黑垆土),胡敏酸在风沙土中运移最快,在黑垆土中运移最慢.     

Kinetics of disaggregation of humic acid in water

The extent of disaggregation of humic acid particles in water was measured as a function of time, initial concentration, pH of the suspension and the temperature. In all experiments the amount of humic acid particles disaggregated was characterized by the corresponding fraction of the suspension, which was able to pass a 0.01 μm membrane filter.It was found that the amount disaggregated after 1000 hours was proportional to the initial concentration of the humic acid particles in the aqueous suspension and increased considerably with the temperature. Decreasing the pH of the suspension from about 6 to zero caused the extent of disaggregation also to decrease continuously.The kinetic measurements revealed that about 3% of the humic acid are disaggregated within 25 hours, 4% within 200 hours and 5% within 1500 hours at a pH around 4. The rates of disaggregation were found to be proportional to the initial concentration of the particles and increased considerably with the temperature.     

Organic matter source discrimination by humic acid characterization: Synchronous scan fluorescence spectroscopy and Ferrate(VI)

In this study, seven soil and sedimentary humic acid samples were analyzed by synchronous scan fluorescence (SSF) spectroscopy. The spectra of these humic acids were compared to each other and characterized, based on three major SSF peaks centered at approximately 281, 367 and 470 nm. Intensity ratios were calculated based on these peaks that were used to numerically assist in source discrimination. All humic acid samples were then reacted with Ferrate(VI) and were again analyzed with SSF. Upon the addition of Ferrate(VI) SSF spectra were obtained which more readily differentiated humic acid source. This method will assist geochemists and water management districts in tracing sources of organic matter to receiving water bodies and may aid in the elucidation of the chemical nature of humic acids.     

混凝絮凝法去除腐质酸的研究

进行了混凝絮凝法去除水中腐殖酸的研究，结果表明，同传统的絮凝剂相比，微生物絮凝剂不仅用量少，去除效果好(去除率可达60％)，而且不产生二次污染，可应用于废水特别是给水中腐殖酸的去除工艺中，对絮凝剂的絮凝机理进行了初步研究，研究表明，微生物絮凝剂去除腐殖酸主要是通过架桥完成的，不同于A12(SO4)3的电中和机理。     

Arsenate removal from underground water by polystyrene-confined hydrated ferric oxide (HFO) nanoparticles:effect of humic acid

Environmental Science and Pollution Research - Arsenic decontamination from groundwater is an urgent but still challenging task. Polystyrene-based hydrated ferric oxide (denoted as D201-HFO)...     

Montmorillonite-Cu(II)/Fe(III) oxides magnetic material as adsorbent for removal of humic acid and its thermal regeneration

In this work, the adsorption features of montmorillonite and the magnetic properties of Cu(II)/Fe(III) oxides were combined in a material to produce magnetic adsorbent, which can be separated from the medium by a simple magnetic process after adsorption. The magnetic material is effective for the removal of humic acid. At pH 6.1, 96% removal was observed from 4.4 mg l(-1) humic acid solution containing 0.02 M NaCl. The adsorption is pH and ionic strength dependent. Adsorption is favored at lower pH values and dissolved NaCl can enhance the adsorption. The adsorption mechanism of humic acid to the magnetic material was suggested to be the ligand exchange reaction between carboxylic groups of humic acid molecules and the magnetic material surface. The magnetic material can be thermally regenerated. The temperature and time required to achieve good regeneration efficiency were determined to be 300 degrees C and 3 h, respectively. The regenerated adsorbent is still magnetic and approximately has as high specific saturation magnetization and good adsorption capacities as the as-prepared adsorbent.     

累托石/腐殖酸微球的制备及其对Cr(Ⅵ)的吸附研究

采用累托石（REC）、腐殖酸（HA）等材料制备微球状吸附剂,考察了累托石、腐殖酸、聚乙烯醇（PVA）、海藻酸钠（SA）、氯化钙等材料的用量对制得的微球吸附性能的影响,通过正交试验确定了微球的最佳制备条件,还考察了微球用量、振荡时间和溶液pH值等因素对微球吸附去除水中Cr(VI)效果的影响。结果表明,采用累托石、腐殖酸、聚乙烯醇等材料可制得高效去除水中六价铬离子的微球状吸附剂,微球的最佳制备条件为：REC 1%,HA 4%,PVA 7%,SA 0.1%,CaCl₂ 0.5%。制得的累托石/腐殖酸微球孔系发达,吸附性能良好。在温度30℃,微球用量0.02 g/mL,振荡时间为2.5 h,pH值为1的条件下,微球对Cr(VI)的吸附效率可达98%以上。