Comparative study of humic acids flocculation with chitosan hydrochloride and chitosan glutamate

Flocculation of dissolved humic acids (HA) and their complexes with metal ions and organic pollutants is a crucial step in drinking water preparation due to significant undesirable effects of humic compounds on water quality. Constant demand for cheap, effective and environmentally friendly flocculants brings about the interest to natural cationic polymers which can be used to neutralize negative charge of humic colloids through polyelectrolyte complexes (PEC) formation. In this work, the interaction of HA with two types of soluble chitosan salts (hydrochloride and glutamate) at different pH and polymer ratios was studied with a focus on electrical charge of PEC formed and effectiveness of color removal in the flocculation process. For both chitosan forms flocculation window was found at pH close to the PEC isoelectric point (pI) in a wide concentration range; however, lower flocculant dose was required when chitosan glutamate was used.     

A study of coagulation mechanisms of polyferric sulfate reacting with humic acid using a fluorescence-quenching method

A fluorescence-quenching method is developed to assess the effect of pH on the coagulation mechanism of humic acids (HA) reacting with metal ions. A polyferric sulfate (PFS) synthesized in our laboratory is adopted as the coagulant to simplify the hydrolysis process and increase the experimental precision. The following results are discovered. When the concentration of PFS increases from 2 to 10 mg/L, the effective pH range of HA removal changes from 4.0-5.0 to 4.0-7.5. At increased coagulation pH, the ferric ions may still react with HA but unable to neutralize the surface charge completely. The residual concentrations of HA measured by fluorescence spectrophotometer are lower than those by TOC, as a consequence of the fluorescence-quenching effect. This demonstrates that the coagulation of HA by PFS at low pH is mainly due to charge-neutralization. The adsorption of the HA on the pre-formed iron hydroxide flocs is accompanied by the dissociation of Fe ions from the floc structure until the equilibrium has been reached, which is evidenced by the presence of the Fe-HA complexes in the solution during adsorption experiment. This is quite different from the characteristics of flocs formed by PFS associated with HA in the coagulation. Within the pH range investigated, the complex-formation and the hydrolysis are the two competitive reactions happened between the hydroxide ions in solution and the functional groups of HA. Therefore, the removal of HA is not caused by adsorbing onto the iron hydroxide resulted from PFS hydrolysis, but through the complex-formation between the PFS and the HA.     

Reduction of chloroform formation potential of humic acid by sonolysis and ultraviolet irradiation

This study is concerned with the changes of chloroform formation potential during the reaction of humic acid (HA) and sodium hypochlorite caused by different oxidative pretreatments: ultraviolet (UV) irradiation, ultrasonic (US) irradiation or combined UV-US irradiations. The UV and US decomposition of a reagent HA in water was investigated. The characterization of the oxidized HA sample by UV absorptiometry, synchronous fluorescence spectroscopy and size exclusion chromatography points a synergetic effect of the combined process. The values of the chlorine demand and chloroform formation potential were conventionally determined after a 96 h reaction at neutral pH. It was found that all applied processes decreased the concentration of chloroform but the highest decrease was observed for the UV-US treatment.     

Characterization of humic substances present in landfill leachates with different landfill ages and its implications

Humic and fulvic acids extracted from landfill leachates were characterized using elemental analysis and various spectroscopic methods. Molecular size distribution of the humic substances (HS) was also determined using batch ultrafiltration technique and permeation coefficient model. The element analysis and spectral features obtained from UV/visible, IR, and 1H and 13C NMR showed that the aromatic character in the leachate HS was relatively lower than that of commercial humic acid (Aldrich Co.), and higher in the HS of older landfill leachate. Fluorescence spectra indicated that humic acids had a relatively higher content of condensed aromatic compounds than the fulvic acids obtained from the same sources, and the spectrum of commercial humic acid showed that aromatic compounds may be present in a much more condensed and complex form. Molecular size distribution data revealed that the leachate humic acids contained a higher percentage of smaller molecules of < 10,000 D, compared with that of the commercial humic acid (45 approximately 49% vs. 33%), and molecular size of the leachate HS had a tendency to increase as landfill age increased. These results indicate that the HS from landfill leachates were in an early stage of humification, and the degree of humification increased as the landfilling age increased, which implies important information on various related researches, such as interactions of HA with pollutants in terrestrial environments, and optimization of leachate treatment processes with respect to landfill age.     

Mobilization and speciation of chromium in compost: a methodological approach

An integral approach to study the mobility of chromium in compost is presented. The approach is based on batch pH dependence leaching tests and the analysis of the leachates for total chromium, chromium(VI) and complexes of chromium(III) with natural organic matter. As leachings are performed with no aggressive reagents (ultrapure water with added nitric acid or potassium hydroxide), the method can be considered a good approach to simulate natural scenarios. The analysis of leachates is complemented with the determination of total chromium and total Cr(VI) in the solid sample. Speciation analysis are done by high performance liquid chromatography with inductively coupled plasma mass spectrometry as detection technique; Cr(VI) is determined by ion chromatography, whereas Cr(III) complexes with natural organic matter by size exclusion chromatography. In the compost studied, Cr(VI) accounted for 6% of the total chromium in the solid, whereas no significant amounts of Cr(VI) were mobilized in the pH range studied (4-10). Chromium is mobilized as Cr(III) bound to organic matter, both to humic and fulvic acids, with an increasing contribution of humic acids at higher pHs.     

Impact of dissolved organic matter on colloid transport in the vadose zone: deterministic approximation of transport deposition coefficients from polymeric coating characteristics

Although numerous studies have been conducted to discern colloid transport and stability processes, the mechanistic understanding of how dissolved organic matter (DOM) affects colloid fate in unsaturated soils (i.e., the vadose zone) remains unclear. This study aims to bridge the gap between the physicochemical responses of colloid complexes and porous media interfaces to solution chemistry, and the effect these changes have on colloid transport and fate. Measurements of adsorbed layer thickness, density, and charge of DOM-colloid complexes and transport experiments with tandem internal process visualization were conducted for key constituents of DOM, humic (HA) and fulvic acids (FA), at acidic, neutral and basic pH and two CaCl₂ concentrations. Polymeric characteristics reveal that, of the two tested DOM constituents, only HA electrosterically stabilizes colloids. This stabilization is highly dependent on solution pH which controls DOM polymer adsorption affinity, and on the presence of Ca⁺² which promotes charge neutralization and inter-particle bridging. Transport experiments indicate that HA improved colloid transport significantly, while FA only marginally affected transport despite having a large effect on particle charge. A transport model with deposition and pore-exclusion parameters fit experimental breakthrough curves well. Trends in deposition coefficients are correlated to the changes in colloid surface potential for bare colloids, but must include adsorbed layer thickness and density for sterically stabilized colloids. Additionally, internal process observations with bright field microscopy reveal that, under optimal conditions for retention, experiments with FA or no DOM promoted colloid retention at solid-water interfaces, while experiments with HA enhanced colloid retention at air-water interfaces, presumably due to partitioning of HA at the air-water interface and/or increased hydrophobic characteristics of HA-colloid complexes.     

Phthalic acid esters in dissolved fractions of landfill leachates

The distribution of phthalic acid esters (PAEs) (including diisobutylphthalate (DIBP), di-n-butylphthalate (DnBP) and bis(2-ethyl)hexylphthalate (DEHP)) in dissolved organic matter (DOM) fractions of leachates from sanitary or bioreactor landfills was evaluated. The leachate DOM was fractionated into humic acid (HA), fulvic acid (FA) and hydrophilic (HyI) fractions. Measurements showed that the PAEs were bound mostly to the HA fraction in leachate, regardless of their landfill age or the presence of leachate recirculation. The PAEs affinity for HA and FA differed considerably relative to the sorption coefficients reported for model compounds. Molecular weight of DOM correlated with PAEs partition in collected leachate samples fractions while aromaticity was a poor predictor. Based on the presence of phenolic, carboxyl or amide groups in DOM fractions, hydrogen bonding is likely to be involved in interactions between PAEs and leachate DOM. The peptide groups, particularly presented in HA fracion, might explain the strong affinity of PAEs for HA. The fluorescence excitation emission matrix contour plots showed that the HyI fractions shared certain similarities with humic substances in terms of molecular structure, which may be one reason why PAEs exhibited a clear sorption to the HyI fractions.     

Anodic stripping voltammetric study of the lability of Cd, Pb, Cu ions sorbed on humic acid particles

The sorption of Cd, Pb and Cu by humic acid particles has been studied at μg l⁻¹ levels using A.S.V. on a Hg film electrode as the measuring technique. The variables examined included amount of solid present (0.01–0.2% w/v), initial metal ion concn (10–100 μg l⁻¹), systems pH (5.3, 6.35, 8.15) and base electrolyte composition. The calculated capacity for specific adsorption of the metal ions was a few mmol M²⁺ kg⁻¹, or less. The apparent lability of part of the sorbed material was examined by analysing the base solution before and after filtering, and by adding Chelex 100 particles to the suspension. Some sorbed Cd²⁺ was A.S.V. labile, another fraction transferred to the resin. The effect of solution reactions on uptake was studied by making the 1 M CH₃COONa base solution 0.2 M in a range of Na⁺ salts (8 different anions), or in carboxylic acid content (5 acids) or in compounds having S-type bonding groups. Formation of complex ions in solution altered the extent of metal ion uptake, and in the case of Cu A.S.V. peak size, shape and position were varied. It is suggested that natural waters containing suspended matter should be analysed by A.S.V. “as received”, as well as after filtration since response differences provide guidance in respect to the lability of sorbed ions.     

Humic acid adsorption and surface charge effects on schwertmannite and goethite in acid sulphate waters

In acid conditions, as in acid mine drainage waters, iron oxide particles are positively charged, attracting negatively charged organic particles present in surrounding natural waters. Schwertmannite (Fe8O8(OH)6SO4) and goethite (alpha-FeOOH) are the most typical iron oxide minerals found in mine effluents. We studied schwertmannite formation in the presence of humic acid. Further, surface charge and adsorption of humic acid on synthetic schwertmannite and goethite surfaces in pH 2-9 and in humic acid concentrations of 0.1-100 mg/L C were examined. Schwertmannite did precipitate despite the presence of humic acid, although it contained more sulphate and had higher specific surface area than ordinary schwertmannite. Specific surface area weighted results showed that schwertmannite and goethite had similar humic acid adsorption capacities. Sulphate was released from schwertmannite surfaces with increasing pH, resulting in an increase in specific surface area. Presence of sulphate in solution decreased the surface charge of schwertmannite and goethite similarly, causing coagulation. In acid conditions (pH 2-3.5), according to the zeta potential, schwertmannite is expected to coagulate even in the presence of high concentrations of humic acid (< or = 100 mg/L C). However, at high humic acid concentrations (10-100 mg/L C) with moderate acid conditions (pH>3.5), both schwertmannite and goethite surfaces are strongly negatively charged (zeta potential < -30 mV) thus posing a risk for colloid stabilization and colloidal transport.     

Evidence from surface tension and fluorescence data of a pyrene-assisted micelle-like assemblage of humic substances

Surface activity and fluorescence of humic substances (HS) and HS/pyrene solutions were monitored under various pH conditions. For HS alone the surface tension of the solutions decreased with increasing acidity, with a minimum at around pH 4. This effect, which is a consequence of an increase in the amphiphilic character of structures, is much more pronounced in humic (HA) than in fulvic acids (FA). The addition of pyrene (0.1 micromolL(-1)) results, for HA, in a marked reduction in the migration of amphiphilic species to the solution surface. FA profiles are not modified in presence of pyrene at that concentration. A decrease in the pyrene I1/I3 ratio in HS solutions shows that below pH 9 pyrene molecules react progressively to the change to a more hydrophobic environment, the greatest effect being observed at around pH 6 to 7. These signals are followed by a significant increase in the pyrene excimer fluorescence (lambda(exc)/lambda(em)=334 nm/450 nm), which is a consequence of the proximity of pyrene molecules. For FA, the I1/I3 decrease is less significant and no excimers develop. This set of effects is explained in view of conformational adjustments of HS, mainly HA, which become arranged in micelle-like domains in aqueous solution, the aromatic moieties being assembled around the pyrene molecules.     

Cadmium adsorption on goethite-coated sand in the presence of humic acid

Heat was employed to coat crystalline goethite onto a quartz sand surface so that the adsorbent properties of the coating could be utilized. The adsorption characteristics of cadmium and humic acid onto goethite-coated sand were examined. Results show that the goethite-coated sand surface had a higher specific surface area and more mesopores than the uncoated sand. The adsorption of both cadmium and humic acid was highly pH-dependent: cadmium adsorption increased with pH, but humic acid adsorption decreased as pH increased. The presence of humic acid resulted in increasing cadmium adsorption in a specific pH range. The order of reacting humic acid with cadmium was found to have a noticeable effect on the final adsorption capacity. The adsorption capacity of cadmium for humic acid that is adsorbed onto goethite-coated sand before reacting with a cadmium system, exceeds that of humic acid that is mixed with cadmium ions before goethite-coated sand is added.     

The roles of natural organic matter in chemical and microbial reduction of ferric iron

Although natural organic matter (NOM) is known to be redox reactive, the roles and effectiveness of specific functional groups of NOM in metal reduction are still a subject of intense investigation. This study entails the investigation of the Fe(III) reduction kinetics and capacity by three fractionated NOM subcomponents in the presence or absence of the dissimilatory metal reducing bacterium Shewanella putrefaciens CN32. Results indicate that NOM was able to reduce Fe(III) abiotically; the reduction was pH-dependent and varied greatly with different fractions of NOM. The polyphenolic-rich NOM-PP fraction exhibited the highest reactivity and oxidation capacity at a low pH (<4) as compared with the carbohydrate-rich NOM-CH fraction and a soil humic acid (soil HA) in reducing Fe(III). However, at a pH>4, soil HA showed a relatively high oxidation capacity, probably resulting from its conformational and solubility changes with an increased solution pH. In the presence of S. putrefaciens CN32, all NOM fractions were found to enhance the microbial reduction of Fe(III) under anaerobic, circumneutral pH conditions. Soil HA was found to be particularly effective in mediating the bioreduction of Fe(III) as compared with the NOM-PP or NOM-CH fractions. NOM-CH was the least effective because it was depleted in both aromatic and polyphenolic organic contents. However, because both soil HA and NOM-PP contain relatively high amounts of aromatic and phenolic compounds, results may indicate that low-molecular-weight polyphenolic organics in NOM-PP were less effective in mediating the bioreduction of Fe(III) at circumneutral pH than the high-molecular-weight polycondensed, conjugated aromatics present in soil HA. These research findings may shed additional light in understanding of the roles and underlying mechanisms of NOM reactions with contaminant metals, radionuclides, and other toxic chemicals in the natural environment.     

Influence of cations on noncovalent interactions between 6-propionyl-2-dimethylaminonaphthalene (PRODAN) and dissolved fulvic and humic acids

The influence of cations (Na(+), Ca(2+) and Mg(2+)) on noncovalent interactions between 6-propionyl-2-dimethylaminonaphthalene (PRODAN) and dissolved fulvic acids (FAs) (Norman landfill leachate fulvic acid (NLFA) and Suwannee River fulvic acid (SRFA)) and dissolved humic acids (HAs) (Suwannee River humic acid (SRHA) and Leonardite humic acid (LHA)) was examined using steady-state fluorescence spectroscopy at pH 4, 7 and 10 as a function of cation concentration (up to 25-100mM). Regardless of pH and cation concentration, PRODAN quenching by FA was unaffected by cations. However, interactions between PRODAN and HA decreased in the presence of cations at pH 7 and 10. Cation concentrations below the HA charge density resulted in the greatest decrease of PRODAN quenching, while very little additional decrease in PRODAN quenching occurred at cation concentrations above the HA charge density. This suggests that as the HA carboxylic acid functional groups form inner sphere complexes with divalent cations, intramolecular interactions result in a contraction of the HA molecular structure, thereby preventing PRODAN from associating with the condensed aromatic, electron accepting moieties inherent within HA molecules and responsible for PRODAN quenching. However, once the HA carboxylic acid functional groups are fully titrated with divalent cations, PRODAN quenching is no longer significantly influenced by the further addition of cations, even though these additional cations facilitate intermolecular interactions between the HA molecules to form supramolecular HA aggregates that can continue to increase in size. Regardless of FA and HA type, pH, cation type and concentration, the lack of blue-shifted fluorescence emission spectra indicated that micelle-like hydrophobic regions, amenable to PRODAN partitioning, were not formed by intra- and intermolecular interactions of FA and HA.     

Comparison of humic acid rejection and flux decline during filtration with negatively charged and uncharged ultrafiltration membranes

Increasingly stringent regulations for drinking water quality have stimulated the ultrafiltration (UF) to become one of the best alternatives replacing conventional drinking water treatment technologies. However, UF is not very effectively to remove humic acid due to the comparatively larger pore size compared to the size of humic acid. Fouling issue is another factor that restricts its widespread application. In this study, rejection of humic acid and flux decline were compared with essentially neutral, negatively charged version of a regenerated cellulose membrane, in which electrostatic interaction was explored for a better humic acid removal and less fouling. Solution environment, including ionic strength, pH and calcium ion concentration, affecting humic acid removal and flux decline on negatively charged and neutral membranes was also compared. Results indicated that the appropriate charge modification on the neutral UF membrane could be an effective way for better removal of NOM and reduction of the membrane fouling due to the electrostatic interactions with the combination effect of membrane pore size. Electrostatic interactions are significant important to achieve high humic acid removal and less fouling, and to improve the water quality and protect people’s health.     

The complexation of protons, aluminium and calcium by aquatic humic substances: A model incorporating binding-site heterogeneity and macroionic effects

A model is presented that describes the competitive binding of protons and metal ions (Al³⁺, AlOH²⁺, Ca²⁺) by humic substances (HS) in the pH range 3–6 and at different ionic strengths, and allows the net humic charge to be calculated. The HS are treated in terms of two types of carboxyl group, together with other more weakly-acidic groups, and the influence of humic (macroionic) charge is taken into account. Eight parameters are involved: total humic acidity, which can be measured directly, content of COOH groups, 4 intrinsic equilibrium constants (2 for H⁺ binding, 2 for metal binding), and 2 parameters accounting for charge effects at different ionic strengths. The model was applied to 4 aquatic humic samples, parameters being estimated from acid-base titration data. The equilibrium contents did not vary greatly among the humic samples, which is consistent with the idea that the functional groups in each sample are chemically the same. The effect of humic charge on complexation varies considerably among the samples. The model was reasonably successful at predicting humic-bound Al in laboratory-prepared solutions and field samples. Calculations based on the model suggest that, (1) Ca²⁺ does not compete significantly with Al for binding to HS under natural acid conditions, and (2) that there is a direct relationship between humic solubility and net humic charge.     

Effect of humic acid on the attachment of Escherichia coli in columns of goethite-coated sand

Though coliform bacteria are used worldwide to indicate faecal pollution of groundwater, the parameters determining the transport of Escherichia coli in aquifers are relatively unknown. To investigate the effect of dissolved organic carbon (DOC) on the attachment of E. coli to saturated goethite-coated sand, we carried out column experiments with E. coli with and without humic acid (HA) in monovalent and divalent salt solutions. To characterize sorption of DOC and attachment of E. coli, we measured the pH of the influent and effluent, the cation concentrations and the zeta potential of particles. Depending on the chemistry of the E. coli suspension, the normalized breakthrough concentrations were over 80 times higher in columns treated with HA compared with columns not treated with HA. However, this difference was not constant: there were time-dependent variations in attachment of E. coli to the collector surface, and in the chemical composition of the bacterial suspension. Reduction in removal occurred because HA altered the surface charge of the collector and also sterically hindered E. coli. In addition, reduction of removal in a CaCl(2) bacterial suspension was probably caused by site-blocking mechanisms between HA and Ca(2+) ions. Our results indicate that in the presence of DOC, the concept of geochemical heterogeneity in explaining attachment of biocolloids has limited relevance.     

Examination of the applicability of cellulose ion exchangers for water and waste water treatment

Three cellulose ion exchangers were examined and it was found that they are able to remove proteins, azodyes, DBS, humic acid, chromate and heavy metal ions (here Cu²⁺). The selectivity of the ion exchangers for removal of these compounds is very high, which explains their ability to remove the examined compounds with high efficiency and capacity, although the three cellulose ion exchangers have only a small capacity expressed as eqv 1⁻². The mass transfer coefficient was found, and it was stated that only the internal mass transfer determines the uptake rate. Theoretical column calculations based upon the found mass transfer coefficient were confirmed by pilot plan experiments.     

Inorganic ligand-modified, colloid-enhanced ultrafiltration: A novel method for removing uranium from aqueous solution

Inorganic ligand-modified, colloid-enhanced ultrafiltration (ILM-CEUF) is as a novel membrane-based separation method for selectively removing target ions from aqueous solution. Traditional colloid-enhanced ultrafiltration (CEUF) is a well-established membrane-based separation technique that can be used to separate metal ions from other aqueous solution components. Ligand-modified, colloid-enhanced ultrafiltration (LM-CEUF) uses organic ligands that selectively complex target ions and also associate with a water-soluble colloid, such as a surfactant micelle or polyelectrolyte. The colloid, associated -ligand, and target ion are then concentrated using an ultrafilter, producing a filtrate with a low concentration of the target ion. While traditional LM-CEUF techniques are able to provide quantitative separations of a variety of ionic pollutants, the high costs of the chelating agents make such techniques nonviable in most remediation schemes. This study investigated the replacement of organic ligands with carbonate for the selective removal of U(VI) from aqueous solution.In slightly to moderately basic solutions containing carbonate, UO₂(CO₃)₃⁴⁻ can be made to dominate the U(VI) speciation. Using poly(diallyldimethylammonium) chloride, the effectiveness and efficiency of ILM-CEUF for removing U(VI) from other aqueous solution components was investigated as a function of carbonate concentration, pH, and ionic strength. Uranium separations of greater than 99.6% were achieved; even in the presence of large excesses of competing ions. The specific separation of U(VI) from Sr²⁺ was also examined.     

Effects of humic acid and electrolytes on photocatalytic reactivity and transport of carbon nanoparticle aggregates in water

The effects of naturally occurring macromolecules such as humic acid (HA) and electrolytes on four fullerene nanoparticle suspensions (i.e., C₆₀, C₆₀(OH)₂₄, single- and multiwall carbon nanotubes) were explored with respect to: (1) characteristics of nanoparticle aggregates, (2) transport of the aggregates through a silica porous media, and (3) production of reactive oxygen species (ROS) from the photosensitized fullerene aggregates. The presence of HA and salts increased the size of aggregates and relative hydrophobicity associated with transport through silica beads, while decreasing ROS production. These data illustrate the importance that transformation of engineered nanomaterials (ENMs) through interactions with aquatic solutes may have in altering the environmental behavior of nanomaterials.     

Changes in humic acid conformation during coagulation with ferric chloride: implications for drinking water treatment

Electrophoretic mobility, pyrene fluorescence, surface tension measurements, transmission electron microscopy on resin-embedded samples, and X-ray microscopy (XRM) were combined to characterize the aggregates formed from humic colloids and hydrolyzed-Fe species under various conditions of pH and mixing. We show that, at low coagulant concentration, the anionic humic network is reorganized upon association with cationic coagulant species to yield more compact structures. In particular, spheroids about 80nm in size are evidenced by XRM at pH 6 and 8 just below the optimal coagulant concentration. Such reorganization of humic colloids does not yield surface-active species, and maintains negative functional groups on the outside of humic/hydrolyzed-Fe complex. We also observe that the humic network remains unaffected by the association with coagulant species up to the restabilization concentration. Upon increasing the coagulant concentration, restructuration becomes limited: indeed, the aggregation of humic acid with hydrolyzed-Fe species can be ascribed to a competition between humic network reconformation rate and collision rate of destabilized colloids. A decrease in stirring favors the shrinkage of humic/hydrolyzed-Fe complexes, which then yields a lower sediment volume. Elemental analyses also reveal that the iron coagulant species are poorly hydrolyzed in the destabilization range. This suggests that destabilization mechanisms such as sweep flocculation or adsorption onto a hydroxyde precipitate are not relevant to our case. A neutralization/complexation destabilization mechanism accompanied by a restructuration of flexible humic network is then proposed to occur in the range of pHs investigated.