Removal of Fulvic Acids from Aqueous Solutions via Surfactant Modified Zeolite

IntroductionNatural organic matter(NOM)is composed of acomplex mixture of organic compounds derived fromliv-ing and dead plants,animals and microorganisms,waste products of animals and microorganisms,andfrom the degradation of the above materials[1].Fulvi…     

Calcium binding by fulvic acids studied by an ion selective electrode an ultrafiltration method

The interaction between Ca(2+) and two well-characterized fulvic acids (Armadale and Laurentide FA) has been studied at 0.100 and 0.010M sodium nitrate using a fixed concentration of fulvic acid (100 ppm) and varying amounts of calcium (0.005-0.020 mmoles). Free calcium concentration was determined by in situ measurements employing a calcium electrode. For Armadale FA, free calcium was additionally determined via an ultrafiltration technique followed by atomic absorption measurements. For both fulvic acids, Ca(2+) binding was observed to be decreased by an increase in the ionic strength of the system. At the lower ionic strength the tendency for binding is dependent on the fulvic acid-to-metal ratio while at the higher ionic strength, the binding is insensitive to changes in the fulvic acid-to-metal ratio (an observation corroborating the contention that calcium binding to humic substances is primarily electrostatic). Comparison of the computed overall complex formation functions shows that values obtained from the ultrafiltration method were higher than those obtained using the calcium electrode. The binding of calcium was similar for the two fulvic acids.     

Evaluation of chlorinated by-products in drinking waters of Central Friuli (Italy)

Drinkable water supplied by aqueducts undergoes preliminar potabilization which, in Italy, is mainly accomplished by chlorine addition. The bactericidal action involved in this process is always accompanied by chlorination and oxidation of organic species (mainly humic and fulvic acids) naturally present in treated waters, so that many disinfection by-products (DBPs) are formed, such as trihalomethanes (THMs) and halo-acetic acids (HAA), which can represent a chemical risk for public health. The aim of this study was the monitoring of DBPs in drinking water disinfected by chlorination, supplied by four different aqueducts of Central Friuli (Italy). DBP evaluations were performed in water samples consisting of both input and output of disinfection plants. The results of analytical determinations were worked out to provide the THM and HAA parameters for disinfected waters, while in feeding waters the following different conventional parameters were adopted: (i) trihalomethanes formation potential (THMFP), (ii) halo-acetic acids formation potential (HAAFP) and (iii) UV absorbance at 254 nm (UV254). The quite moderate content of chlorinated products found in all samples considered highlighted the excellent quality of potabilized waters available in Central Friuli. Moreover, our results confirmed that the majority of DBPs formed when chlorine is used for water disinfection consists of THMs, while chlorites and chlorates prevailed when potabilization is accomplished by using chlorine dioxide. Finally, simple UV254 monitoring turned out to be a profitable approach for the determination of chlorinated by-products only when THMs prevail among DBPs.     

Molecular structure of fulvic acids by electrospray with quadrupole time-of-flight mass spectrometry

Characterisation of the molecular structure of aquatic fulvic acids (FA) has been performed using a quadrupole time-of-flight (Q-TOF) mass spectrometer equipped with an electrospray ionisation interface. Molecular masses centred around 450 Da and sinusoidal spectral distributions have been obtained for all fulvic acids. Tandem mass spectrometry (MS/MS) experiments showed losses of 18 Da (H(2)O) and 44 Da (CO(2)), and possible molecular structures were determined for the first time to our knowledge. A methodology is reported for evaluating the average elemental composition of FA from high-resolution mass spectra by processing post-acquisition data calculations using molecular size distributions and atomic compositions of ions. The results are found to be consistent with elemental analysis data.     

Complexation of Eu and Tb with fulvic acids as studied by time-resolved laser-induced fluorescence

Complexation of Eu and Tb with fulvic acids (FA) has been studied by time-resolved laser-induced fluorescence. The lanthanide species are excited by a pulsed Xe/Cl excimer laser and the short-lived luminescence of the fulvic acids is eliminated by time gating. The conditional binding constants (K') and the total metal-binding capacities of the fulvic acids have been determined from the equilibrium titration curves. No significant variations of the log K' values (about 6) have been found in the pH range investigated (2.7, 5.5, 6.5) at ionic strengths of 0.1 and 1M (NaClO(4)). An inverse relationship of K' to total metal concentration is observed. Substitution of Eu for Al has been found to depress the fluorescence signal of the Eu-FA complex. The binding constants of Al(3+) and Eu(3+), derived from the competition experiments, are of the same order of magnitude. The effect of competition on metal binding and trace-metal transport is discussed.     

Study of the acid–base properties of fulvic acid-like substances extracted from senescent leaves of eucalyptus and oak

The acid-base properties of two fulvic acids (FA) extracted from senescent leaves of eucalyptus and oak were characterized by carrying out potentiometric titrations at two FA concentrations and four ionic strengths (0.005 M <[KNO(3)] <1.0 M). Experimental data were analyzed by means of the master curve approach, which includes an electrostatic spherical double layer model, and the Langmuir-Freundlich isotherm was used to fit the data. The contribution of the electrostatic effect to the proton binding reaction was lower than that observed for soil fulvic acids. The chemical heterogeneity of both samples was described by two acid sites with p Ks of about 4 and 7.5, the most abundant being the carboxylic site of p K = 4.     

Investigation of fulvic acids from peat using capillary electrophoresis (CE)

The aim of this work was to characterize the fulvic acids (FA) extracted from peat by use of capillary electrophoresis (CE). Two FA extracts have been obtained using two different extractants (0.1 M NaOH and 0.1 M NaOH plus 0.1 M Na₄P₂O₇, Na+PP). The CE runs wre performed using a coated silica capillary, and several buffer solutions at different PH values. The results obtained show that the Fa extracts may be well characterized by CE even if the isolelectric point of the fulvic compounds is very low. The best fractionation has been obtained using a buffer borate at PH 8.9 as funning buffer. The charcterization of the two extracts also showed some important differences between the NaOH extract and the Na+PP extract.     

Hydration of humic and fulvic acids studied by DSC

Qualitative and quantitative aspects of hydration of four humic acids (HA) and three fulvic acids (FA) originating from different sources were investigated. DSC experiments at subambient temperatures were carried out in order to monitor differences in ice behavior originating from freezable water surrounding humic molecules. It was found that kinetic effects play a significant role in hydration processes of both HA and FA. In fact, the hydration took part over 21?days which was detected as a progressive decrease in ice melting enthalpy. Simultaneously, the peak shapes and positions changed indicating structural changes in the physical structure of the humic substances. In case of FA, the dependency of melting enthalpy on water concentration showed a linear trend resembling a complete hydration previously observed for water-soluble hydrophilic polymers. In contrast, the melting enthalpy of some HA increased in a step-like way with increasing water content, suggesting preservation of original hydrophobic scaffold during the hydration. The differences between the rather young FA and the rather old HA lead to the conclusion that water can play a significant role in processes of humification. We assume that separation of hydrophobic and hydrophilic domains and thus increase in nanoscale heterogeneity represents an important physical contribution to the overall humification process. It was also demonstrated that the higher content of oxygen in humic molecules is not the only indicator of higher water holding capacity. Instead the porosity of humic matrix seems to contribute as additional parameter into these processes.     

玉米秸秆堆腐过程中形成富里酸的结构分析

采用傅里叶变换红外光谱及＾１Ｈ和＾１３Ｃ核磁共振波谱对玉米秸秆堆腐过程中形成的富里酸的结构进行了表征。结果表明,玉米秸秆腐解过程中形成的富里酸包括羧基或羰基基团,芳香结构,烷基片断和碳水化合物结构。     

Advances in identification of plant gums in cultural heritage by thermally assisted hydrolysis and methylation

Plant gums are present in works of art as binding media for watercolours and adhesives for cellulosic substrates. Thermally assisted hydrolysis and methylation (THM) in combination with analytical pyrolysis coupled to GC/MS has been applied to the characterisation of plant gums typically used in artworks. THM products from standard samples of arabic gum, tragacanth gum and cherry gum were characterised. The main products identified are permethylated and partially methylated aldonic acids, characteristic of specific epimeric sugars. Aldonic acids were formed by alkaline hydrolysis of free reducing sugars and of reducing polysaccharide terminal groups, while methylation occurs during pyrolysis. The presence of these characteristic markers allows gum identification. A systematic analysis of all the parameters that can affect the marker yields was performed. In particular, the influence of pyrolysis temperature, reagent concentration and contact time between tetramethylammonium hydroxide and sample were studied, and different kinds of sample preparation procedures were tested. Some analyses on real watercolours were performed, and gum binders were classified using the peak area ratio of the main monosaccharide markers.     

Trace humic and fulvic acid determination in natural water by cloud point extraction/preconcentration using non-ionic and cationic surfactants with FI-UV detection

A preconcentration and determination method for humic and fulvic acids at trace levels in natural water samples was developed. Cloud point extraction was successfully employed for the preconcentration of humic acid (HA) and fulvic acid (FA) prior to the determination by using a flow injection (FI) system coupled to a spectrophotometric UV-Vis detector. The quantitative extraction of HA and FA within the pH range 1-12 was obtained by neutralization of the anionic charge on the humic substances with a cationic surfactant, hexadecyltrimethylammonium bromide (CTAB). This generated a hydrophobic species that was subsequently incorporated (solubilized) into the micelles of a non-ionic surfactant polyethylene glycol, tert-octylphenyl ether (Triton X-114). The FI method for HA and FA determination was developed by injection of 100 microl of the extracted surfactant-rich phase using an HPLC pump with spectrophotometric detection at 350 nm. A 50 ml sample solution preconcentration allowed an enrichment factor of 167. The limit of detection (LOD) obtained under the optimal conditions was 5 microg l(-1). The precision for ten replicate determinations at 0.2 mg l(-1) HA was 3.1% relative standard deviation (RSD), calculated from the peak heights. The calibration using the preconcentration system for HA and FA was linear with a correlation coefficient (r2) of 0.9997 at levels near the detection limits up to at least 1 mg l(-1). The method was successfully applied to the determination of HA and FA in natural water samples (river water).     

Sorption of Fulvic Acids from the Neva River on Anion Exchangers Based on Styrene-Divinylbenzene Copolymer

Sorption of fulvic acids (FA) on anion exchangers based on styrene-divinylbenzene copolymerwas studied.     

Molecular and quantitative aspects of the chemistry of fulvic acid and its interactions with metal ions and organic chemicals : Part II. The fluorescence spectroscopy approach

Information in the literature on the use of fluorescence spectroscopy for the study of the chemistry of fulvic acid and its interactions with metal ions and organic chemicals is discussed. Basic principles, instrumentation, procedures, methodology and limitations of the fluorescence technique and the fluorescence polarization method are briefly summarized. This is followed by an extended discussion on the direct information that fluorescence spectra can furnish on the properties and nature of fluorescing structures in fulvic acids. The effects of molecular parameters and environmental factors (molecular weight, concentration, pH, ionic strength, temperature and redox potential) on the fluorescence behaviour of fulvic acids are discussed. Particular attention is devoted to the indirect information that fluorescence quenching and fluorescence polarization studies provide on molecular and quantitative aspects of the chemistry of fulvic acid in solution, especially in relation to molecular conformation and binding with metal ions and organic chemicals. The potential advantage of this non-separative, non-destructive technique for the study of environmental samples such as fulvic acids is emphasized.     

饮用水新型含氮消毒副产物卤乙酰胺稳定性研究

饮用水氯化消毒工艺向氯胺消毒工艺的转变, 降低了三卤甲烷(THM)和卤乙酸(HAA)等消毒副产物(DBP)的浓度, 但增加了毒性更强的含氮消毒副产物(N-DBP)含量, 卤乙酰胺(HAcAm)便是其中的代表. 本研究结合线性自由能关系(LFER)理论, 考察了HAcAm在不同pH条件下的水解特性, 以及不同氯投加量条件下的氯化特性, 并探讨了HAcAm的水解和氯化反应路径. 结果表明, 在较强的酸性条件下(pH＝4)二氯乙酰胺(DCAcAm)将发生水解反应, pH＝5时DCAcAm较为稳定, 三氯乙酰胺(TCAcAm)在酸性条件下未产生明显的水解现象; 碱性环境中TCAcAm和DCAcAm皆发生明显水解反应, 反应符合一级动力学, 保存DCAcAm和TCAcAm水样时需调pH至5左右. 氯化消毒会产生较高浓度的THM和HAA, 但可能会缩减毒性更强的HAcAm等N-DBP在饮用水中的含量. pH＝10时TCAcAm水解后快速生成三氯乙酸(TCAA); 而对于氯化反应, TCAcAm与HOCl反应生成较为稳定的中间产物Cl-N-TCAcAm, 当HOCl浓度较高时, Cl-N-TCAcAm进一步与HOCl反应生成TCAA.     

Purification of soluble fulvic acid low concentrations by a diafiltration technique

The purification of soluble fulvic acids (FA) based on a diafiltration technique is carried out on antarctic water and snow samples, characterised by low humic compound content (0.1-0.8 mg/l). Results are compared with those of FA purified with the dialysis technique that, together with ion-exchange resins, performs an often used purification process. With the adopted procedure it is possible to minimise the high content of inorganic salts deriving in part from the isolation method XAD-8 adopted, as shown by FTIR, elemental and thermogravimetric analysis.     

Study of the acid-base properties of leaf litter extracts

The acid-base properties of four leaf litter extracts, LLE (eucalyptus, fern, oak and chestnut coverture), were characterized by synchronous fluorescence (SyF) spectroscopy and compared with those of two fulvic acids (FA) extracted from two different horizons (0–5 and 5–15 cm) of an oak forest soil. The characterization was based on the variation with the pH of the properties of the fluorescent structures present in the samples, which function as probes and provide a macroscopic image of their acid-base properties. These sets of SyF spectra collected as a function of the pH show fingerprinting potential. They were treated by a self-modeling curve resolution procedure, evolving factor analysis with a gradient concentration window (EFA-GCW), to reduce the raw spectral data to the number of components, their spectra, and SyF intensity profiles (pH distribution diagrams). Four acid-base systems were detected for all samples of LLE and FA with pKas ranging from 2.5 to 10.0 (pKas about 3, 5, 7 and 9, except for the fern LLE sample which showed pKas about 5, 7, 9 and 10). A similarity analysis of the spectra of the components, performed by cluster analysis, showed that the most acidic fluorescent structures of the LLE are not similar to those of the soil FA, but the less acidic are. Received: 20 June 1997 / Revised: 11 November 1997 / Accepted: 16 November 1977     

Interactions of anionic dyes with silica-aminopropyl 1. A quantitative multivariate analysis of equilibrium adsorption and adsorption Gibbs free energies

In this work silica-aminopropyl (Sil-NH2) was synthesized and employed to evaluate the quantitative roles of temperature, pH, dye concentration, and Hg(II) or anionic surfactant SDB interferents in the adsorptions of blue and red remazol dyes in aqueous medium using four distinct 2(4) factorial designs. The results were analyzed statistically using multiple regressions, Student's t-test, analysis of variance, and F-test. Polynomial modelings were used to define the most important factors affecting dye adsorption. The results indicate that the principal effects of dye concentration and pH, as well as most of the interactions of all factors, are statistically very important in relation to the equilibrium adsorption quantities. However, the adsorption Gibbs free energies are influenced, in general, only by pH, dye concentration, and some binary interactions. Temperature changes do not affect the deltaG values significantly.     

A speciation methodology to study the contributions of humic-like and fulvic-like acids to the mobilization of metals from compost using size exclusion chromatography-ultraviolet absorption-inductively coupled plasma mass spectrometry and deconvolution analysis

High performance size-exclusion chromatography (HP-SEC) with UV absorption for organic matter detection and inductively coupled plasma mass spectrometry (ICP-MS) for elemental detection have been used to study the mobilization of metals from compost as a function of pH and the molecular mass of their complexes with dissolved organic matter (DOM). Due to its heterogeneous nature, organic matter mobilized from compost shows a continuous distribution of molecular masses in the range studied (up to 80 kDa). In order to differentiate between the contribution of humic and fulvic acids (FA) to the organic matter mobilized in the pH range 5-10, their UV absorption chromatographic profiles have been deconvoluted with respect to the adjusted gaussian profiles of the humic and fulvic acids isolated from compost. Results show a preponderant contribution of fulvic acids at low pH values and an increasing percentage of humic acids (HA) mobilized at basic pH (up to 49% of total DOM at pH 10). A similar deconvolution procedure has been applied to the ICP-MS chromatograms of selected metals (Co, Cu, Pb and Bi). In general, both fulvic and humic acids contribute to the mobilization of divalent transition metals, such as copper or cobalt, whereas bismuth or lead are preferably associated to humic acids. Non-humic substances (HS) also contribute to the mobilization of cations, especially at acidic pHs. These conclusions have been extended to different elements based on deconvolution analysis results at pH 7.     

Factorial analysis of a chemiluminescence system for bromate detection in water

A chemiluminescent flow system for bromate detection, based on the reaction of bromate with sulphite in acid medium and using the steroid hydrocortisone as sensitiser, was studied. A factorial analysis strategy for the study of the effect on the system response of the experimental factors, flow rates of two pumps (Q₁ — acid sulphite plus hydrocortisone aqueous solution; Q₂ — carrier, water), sample injection volume (V_L), reactor volume (V_R), sulphite concentration (C_S), hydrocortisone concentration (C_H) and acid concentration (C_A), was used. Screening analysis of the system performance was made using Plackett Burman designs. The system optimisation procedure was achieved by three levels three factors full factorial designs. V_L and C_H are the most significant factors — a quadratic C_H term was also observed to be significant. The optimised system responded linearly (logarithm of the detector signal as function of the logarithm of the bromate concentration) in the concentration range between 3.6×10⁻⁷ and 5.0×10⁻⁴ M with a limit of detection of about 8.0×10⁻⁸ M (about 10 microg/l). An analysis of some interfering ions was made and it was suggested that bromide and chloride begin to quench chemiluminescence when they are in a 10-fold excess relatively to bromate concentration.     

Study of the complexation of Cu(II) by fulvic acids extracted from a sewage sludge and its compost

 The complexation of Cu(II) by two samples of fulvic acids (FA) extracted from the raw sewage sludge (RsFA) of a waste water processing plant and from the composted sludge (CsFA) obtained upon aerobical digestion was studied at pH 6.0. Synchronous molecular fluorescence spectroscopy was used to monitor the association of FA with Cu(II) and a self-modelling mixture analysis method (SIMPLISMA) was used to preprocess the spectral data to calculate the number of components with different quenching profiles as function of the Cu(II) concentration and their spectra. The stability constants and a rough estimation of the binding site concentrations were obtained by a Stern-Volmer analysis, by a non-linear least-square method and by a linear procedure. The analysis of the SyF spectra allowed the identification of two binding sites for both samples. The logarithm of the conditional stability constant corresponding to the 1:1 complex formed between the stronger binding site and Cu(II) is about 4 for both samples. Received: 22 April 1996 / Revised: 5 August 1996 / Accepted: 7 August 1996