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.     

Investigation of metal ions binding of humic substances using fluorescence emission and synchronous-scan spectroscopy

The binding site interactions of IHSS humic substances, Suwannee River Humic Acid, Suwannee River Fulvic Acid, Nordic Fulvic Acid, and Aldrich Humic Acid with various metals ions and a herbicide, methyl viologen were investigated using fluorescence emission and synchronous-scan spectroscopy. The metal ions used were, Fe(III), Cr(III), Cr(VI), Pb(II), Cu(II) and Ni(II). Stern-Volmer constants, Ksv for these quenchers were determined at pH 4 and 8 using an ionic strength of 0.1 M. For all four humic substances, and at both pH studied, Fe(III) was found to be the most efficient quencher. Quenching efficiency was found to be 3-10 times higher at pH 8. The bimolecular quenching rate constants were found to exceed the maximum considered for diffusion controlled interactions, and indicate that the fluorophore and quencher are in close physical association. Synchronous-scan spectra were found to change with pH and provided useful information on binding site interactions between humic substances and these quenchers.     

Investigation of metal ions binding of humic substances using fluorescence emission and synchronous‐scan spectroscopy

Abstract

The binding site interactions of IHSS humic substances, Suwannee River Humic Acid, Suwannee River Fulvic Acid, Nordic Fulvic Acid, and Aldrich Humic Acid with various metals ions and a herbicide, methyl viologen were investigated using fluorescence emission and synchronous‐scan spectroscopy. The metal ions used were, Fe(III), Cr(III), Cr(VI), Pb(II), Cu(II) and Ni(II). Stern‐Volmer constants, K_SV for these quenchers were determined at pH 4 and 8 using an ionic strength of 0.1M. For all four humic substances, and at both pH studied, Fe(III) was found to be the most efficient quencher. Quenching efficiency was found to be 3–10 times higher at pH 8. The bimolecular quenching rate constants were found to exceed the maximum considered for diffusion controlled interactions, and indicate that the fluorophore and quencher are in close physical association. Synchronous‐scan spectra were found to change with pH and provided useful information on binding site interactions between humic substances and these quenchers.     

Reactions of compost-derived humic substances with lead, copper, cadmium, and zinc

Thermodynamic stability constants of the formation of complexes from the reactions of humic substances with various metals are usually used as parameters to judge the reactivities of both humic substances and metals. However, in calculating the thermodynamic stability constants, complicated processes for the acquisition of activities of components in reactions are absolutely inevitable. In this study, we investigated the average conditional concentration quotients of the complexes formed from the reaction of metals with humic substances and the relations of these quotients to thermodynamic stability constants. The characterized humic substances including HA (MW>1,000), FA (MW>1,000), and FA (MW<1,000) extracted from a swine compost were prepared to react with Pb, Cu, Cd, and Zn at 25 degrees C and at pH 4.00 and 6.50. Reactions of HA (MW>1,000), FA (MW>1,000), and FA (MW<1,000) with the four metals were carried out at 1:0.1, 1:0.5, 1:1, 1:5, and 1:10 ligand:metal stoichiometry. The concentrations of the free ions of Pb, Cu, Cd, and Zn in the reaction systems of metal-HA suspensions and metal-FA solutions were measured by anodic stripping voltammetry (ASV). The sequence of the average conditional concentration quotients of the formed complexes from the reaction of humic substances with metals was FA(MW<1,000)>FA(MW>1,000)>HA(MW>1,000), showing the relative reactivities of the fractions of swine compost-derived humic substances. The sequence of reacting metals with humic substances was Pb>Cu>Cd>Zn, which is in good agreement with the sequence reported by judging the thermodynamic stability constants. The average conditional concentration quotients of the formed complexes from the reaction of humic substances with metals were thus useful parameters that can be directly related to thermodynamic stability constants and other parameters.     

Removal of alachlor from water by catalyzed ozonation in the presence of Fe2+, Mn2+, and humic substances

The effects of Fe(II), Mn(III) and humic substances on the catalyzed ozonation of alachlor, an endocrine disruptor were investigated. Results revealed that small amounts of Fe(II), Mn(II), and humic substances could enhance the ozonation of alachlor, but larger amounts of them would retard the oxidation. These results were successfully identified by an electron paramagnetic resonance (EPR) spectroscopy spin-trapping method that could quantify hydroxyl radicals. The production of hydroxyl radicals was obviously increased with the increasing of Fe(II) concentration, which contributed to enhance ozonation at low concentrations. But the excess Fe(II) consumed some of the radicals when it was added at a higher concentration (1.5 mg/L). However, no obvious radicals were observed when a different amount of Mn(II) was used, and the catalytic ozonation of alachlor by Mn(II) mainly followed the mechanism of "active sites created on the surface of MnO2." The radical pathway was followed when alachlor was ozonated with different concentrations of humic substances because of its radical initiating, promoting, and inhibiting effects.     

Effects of organic acids on adsorption of lead onto montmorillonite,goethite and humic acid

Adsorption isotherms for Pb onto six soil components (quartz, feldspar, kaolinite, montmorillonite, goethite and humic acid) were studied. The influence of pH, EDTA and citric acid on the adsorption of Pb onto montmorillonite, goethite and humic acid were considered. Results indicate that the experimental data fit the Langmuir Adsorption Isotherm. The adsorption capacity for Pb at pH 6 was found to be in the order: humic acid (22.7 mg g(-1)) > goethite (11.04 mg g(-1)) > montmorillonite (10.4 mg g(-1)) > kaolinite (0.91 mg g(-1)) > feldspar (0.503 mg g(-1)) > quartz (0.148 mg g(-1)). Generally, the amount of Pb adsorbed onto montmorillonite, goethite and humic acid decreased with increasing concentrations of EDTA and citric acid and with increases in alkality. However, there were two exceptions: (1) addition of citric acid increased the amount of Pb adsorbed onto humic acid; and (2) the amount of Pb adsorbed onto goethite decreased with increasing pH in the presence of EDTA. Some mechanisms involved in the adsorption reactions are discussed.     

Removal of Alachlor from Water by Catalyzed Ozonation in the Presence of Fe2+, Mn2+, and Humic Substances

Abstract

The effects of Fe(II), Mn(II) and humic substances on the catalyzed ozonation of alachlor, an endocrine disruptor were investigated. Results revealed that small amounts of Fe(II), Mn(II), and humic substances could enhance the ozonation of alachlor, but larger amounts of them would retard the oxidation. These results were successfully identified by an electron paramagnetic resonance (EPR) spectroscopy/spin-trapping method that could quantify hydroxyl radicals. The production of hydroxyl radicals was obviously increased with the increasing of Fe(II) concentration, which contributed to enhance ozonation at low concentrations. But the excess Fe(II) consumed some of the radicals when it was added at a higher concentration (1.5 mg/L). However, no obvious radicals were observed when a different amount of Mn(II) was used, and the catalytic ozonation of alachlor by Mn(II) mainly followed the mechanism of “active sites created on the surface of MnO₂.” The radical pathway was followed when alachlor was ozonated with different concentrations of humic substances because of its radical initiating, promoting, and inhibiting effects.     

Copper binding by peat fulvic and humic acids extracted from two horizons of an ombrotrophic peat bog

We studied the binding of Cu(II) to humic acids and fulvic acids extracted from two horizons of an ombrotrophic peat bog by metal titration experiments at pH 4.5, 5.0, 5.5, and 6.0 and 0.1 M KNO3 ionic strength. Free metal ion concentrations in solution were measured using an ion selective electrode. The amounts of base required to maintain constant pH conditions were recorded and used to calculate H+/Cu2+ exchange ratios. The amount of Cu(II) bound to the humic fractions was greater than the amount bound to the fulvic fractions and only at the highest concentrations of metal ion the amount of Cu(II) sorbed by both fractions became equal. The proton to metal ion exchange ratios are similar for all humic substances, with values ranging from 1.0 to 2.0, and decreasing with increased pH. The amount of Cu(II) bound is practically independent of the horizon from which the sample was extracted. The results indicate that the humic substances show similar cation binding behaviour, despite the differences in chemical composition. The copper binding data are quantitatively described with the NICA-Donnan model, which allows to characterize only the carboxylic type binding sites. The values of the binding constants are higher for the humic acids than for the fulvic acids.     

Thermodynamics of metal cation binding by a solid soil-derived humic acid: binding of Fe(III), Pb(II), and Cu(II)

Metal binding and release by solid humic acids (HAs) in soils and sediments can affect metal mobility and bioavailability. Isotherms for tight binding of Fe(III), Pb(II) and Cu(II) by a solid humic acid at pH2.0 fit the Langmuir binding model. Low pH was chosen to protonate the HA carboxylate groups and avoid metal cation hydrolysis. Binding of Fe(III), Pb(II) and Cu(II) occurs in one detectable step labeled A. Site capacities nu(A) are temperature-independent from 10.0 to 40.0 degrees C and point to binding by charge-neutralization to form solid complexes M(OOC-R)(n)(s), where n appears to be 2 for Pb(II) and 3 for Fe(III). Thermodynamic data pairs (DeltaH(A), DeltaS(A)) for metal binding are linearly correlated with previous data for Ca(II), Co(II) and Mg(II) binding by solid HAs.     

Formation of chloroacetic acids from soil,humic acid and phenolic moieties

The mechanism of formation of chloroacetates, which are important toxic environmental substances, has been controversial. Whereas the anthropogenic production has been well established, a natural formation has also been suggested. In this study the natural formation of chloroacetic acids from soil, as well as from humic material which is present in soil and from phenolic model substances has been investigated. It is shown that chloroacetates are formed from humic material with a linear relationship between the amount of humic acid used and chloroacetates found. More dichloroacetate (DCA) than trichloroacetate (TCA) is produced. The addition of Fe(2+), Fe(3+) and H(2)O(2) leads to an increased yield. NaCl was added as a source of chloride. We further examined the relationship between the structure and reactivity of phenolic substances, which can be considered as monomeric units of humic acids. Ethoxyphenol with built-in ethyl groups forms large amounts of DCA and TCA. The experiments with phenoxyacetic acid yielded large amounts of monochloroacetate (MCA). With other phenolic substances a ring cleavage was observed. Our investigations indicate that chloroacetates are formed abiotically from humic material and soils in addition to their known biotic mode of formation.     

Effect of metal ions and humic acid on the dechlorination of tetrachloroethylene by zerovalent iron

The dechlorination of tetrachloroethylene (PCE) by zerovalent iron (Fe(0)) in the presence of metal ions and humic acid was investigated. In the absence of metal ion and humic acid, 64% of the initial PCE was dechlorinated after 125 h with the production of ethane and ethene as the major end products. The dechlorination followed pseudo-first-order kinetics and the normalized surface rate constant (k(SA)) for PCE dechlorination was (3.43+/-0.61)x10(-3)lm(-2)h(-1). Addition of metal ions enhanced the dechlorination efficiency and rate of PCE, and the enhancement effect followed the order Ni(II)>Cu(II)>Co(II). The k(SA) for PCE dechlorination in the presence of metal ions were 2-84 times higher than that in the absence of metal ions. X-ray photoelectron spectroscopy (XPS) showed that Cu(II) and Ni(II) were reduced by Fe(0) to zerovalent metals, and resulted in the formation of bimetallic system to accelerate the dechlorination reaction. On the contrary, humic acid out-competed the reactive sites on iron surface with PCE, and subsequently decreased the dechlorination efficiency and rate of PCE by Fe(0). However, the reactivity of Fe(0) for PCE dechlorination in the presence of metal ions and humic acid increased by a factor of 3-161 when compared to the iron system containing humic acid alone. Since humic acid and metal ions are the most often found co-existing compounds in the contaminated aquifers with chlorinated hydrocarbons, results obtained in this study is useful to better understand the feasibility of using Fe(0) for long-term application to the remediation of contaminated sites.     

Colloidal diatomite, radionickel, and humic substance interaction: a combined batch, XPS, and EXAFS investigation

This work determined the influence of humic acid (HA) and fulvic acid (FA) on the interaction mechanism and microstructure of Ni(II) onto diatomite by using batch experiments, X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS) methods. Macroscopic and spectroscopic experiments have been combined to see the evolution of the interaction mechanism and microstructure of Ni(II) in the presence of HA/FA as compared with that in the absence of HA/FA. The results indicated that the interaction of Ni(II) with diatomite presents the expected solution pH edge at 7.0, which is modified by addition of HA/FA. In the presence of HA/FA, the interaction of Ni(II) with diatomite increased below solution pH 7.0, while Ni(II) interaction decreased above solution pH 7.0. XPS analysis suggested that the enrichment of Ni(II) onto diatomite may be due to the formation of (≡SO)₂Ni. EXAFS results showed that binary surface complexes and ternary surface complexes of Ni(II) can be simultaneously formed in the presence of HA/FA, whereas only binary surface complexes of Ni(II) are formed in the absence of HA/FA, which contribute to the enhanced Ni(II) uptake at low pH values. The results observed in this work are important for the evaluation of Ni(II) and related radionuclide physicochemical behavior in the natural soil and water environment.     

Effects of humic substances on the decomposition of 2,4-dichlorophenol by ozone after extraction from water into acetic acid through activated carbon

The objectives of this study are to clarify the behavior of humic substances throughout the processes of 2,4-dichlorophenol (2,4-DCP) adsorption on granular activated carbon (GAC) from water and extraction into acetic acid, and the influence of the extracted humic substances on the decomposition of 2,4-DCP by ozone in the acetic acid. The adsorption capacity of GAC for 2,4-DCP was not influenced by the humic substances preloaded to have equilibrium concentration of 24.9mg Cl(-1) (14.5mg Cg(-1)). The adsorption capacity of GAC for 2,4-DCP decreased to one tenth of new GAC after the first adsorption-extraction step because of only 16% desorption in the first step. However, 2,4-DCP adsorbed on GAC was completely extracted after the second step suggesting that GAC can be used as adsorbent to transfer 2,4-DCP from water to acetic acid. The concentration ratio of 2,4-DCP from water into acetic acid was around 2x10(5), whereas the concentration ratio of humic substances was about 3.5, indicating that 2,4-DCP was selectively adsorbed and extracted by this system. The first order degradation rate constant for 2,4-DCP by ozone in acetic acid increased with the addition of humic substances. The rate constant with 16mg Cl(-1) of humic substances was 2.6 times as high as that without humic substances. Humic substances behaved as a promoter for the degradation of 2,4-DCP by ozone.     

Organic compounds adsorption onto activated carbon: the effect of association between dissolved humic substances and pesticides

The quantitative determination of pesticide binding to dissolved humic substances is relevant to both water treatment operation using activated carbon adsorption process and the application of transport models that predict the environmental distribution patterns of a given hydrophobic contaminant. In this study and in a first set of experiments, the extent of binding between (i) three pesticides of environmental concern, aldicarb, lindane and pentachlorophenol, and (ii) dissolved commercial humic acid and soil extracted fulvic acid, was determined using dialysis experiments and water solubility enhancement tests. In a second set of experiments, the influence of dissolved humic substances or pesticide on the retention of the other co-adsorbate onto activated carbon was investigated in binary systems. It was found that association was negligible for aldicarb and that the pesticide sorption onto activated carbon was not affected by humic acid (8.5 mg liter(-1) DOC). The association constants K for lindane and pentachlorophenol were identical in the presence of fulvic acid (logK=4.1) but lower than that observed with humic acid. In the presence of humic acid, binding affinity for pentachlorophenol (logK=4.6) was higher than the one observed for lindane (logK=4.4), despite its much higher water solubility. This observation suggests that the aromatic character of the pentachlorophenol molecule contributes to association interactions with humic acid. From co-adsorption experiments onto activated carbon it was found that fulvic acid (7.7 mg litre(-1) DOC) slightly enhances sorption kinetics of pentachlorophenol. Lindane (1 mg litre(-1)) does not affect sorption kinetics for fulvic acid but markedly enhances both the sorption kinetics and adsorptive capacity for humic acid. Activated carbon retention of dissolved humic substances or pesticide appears to be enhanced by the association potential that exists between these co-adsorbates in some binary systems.     

Potential availability of heavy metals to phytoextraction from contaminated soils induced by exogenous humic substances

Effective phytoremediation of soils contaminated by heavy metals depends on their availability to plant uptake that, in turn, may be influenced by either the existing soil humus or an exogenous humic matter. We amended an organic and a mineral soil with an exogenous humic acid (HA) in order to enhance the soil organic carbon (SOC) content by 1% and 2%. The treated soils were further enriched with heavy metals (Cu, Pb, Cd, Zn, Ni) to a concentration of 0, 10, 20, and 40 microg/g for each metal and allowed to age at room temperature for 1 and 2 months. After each period, they were extracted for readily soluble and exchangeable (2.5% acetic acid), plant-available (DTPA, Diethylentriaminepentaacetic acid), and occluded (1 N HNO(3)) metal species. Addition of HA generally reduced the extractability of the soluble and exchangeable forms of metals. This effect was directly related to the amount of added HA and increased with ageing time. Conversely, the potentially plant-available metals extracted with DTPA were generally larger with increasing additions of exogenous HA solutions. This was attributed to the formation of metal-humic complexes, which ensured a temporary bioavailability of metals and prevented their rapid transformation into insoluble species. Extractions with 1 N HNO(3) further indicated that the added metals were present in complexes with HA. The observed effects appeared to also depend on the amount of native SOC and its structural changes with ageing. The results suggest that soil amendments with exogenous humic matter may accelerate the phytoremediation of heavy metals from contaminated soil, while concomitantly prevent their environmental mobility.     

Removal of organic polyelectrolytes and their metal complexes by adsorption onto xonotlite

Natural organic polyelectrolytes (humic and fulvic acids) and their metal complexes were removed by adsorption onto xonotlite. The removal percentages of humic and fulvic acids by xonotlite were approximately 80% and 30%, respectively. Humic acid removal from solution by adsorption onto xonotlite took place more readily than fulvic acid removal. The molecular weight distributions of the humic substances remaining in solution after adsorption with the xonotlite were measured with size exclusion chromatography. A comparison of molecular weight distributions demonstrated conclusively that large molecular weight components were adsorbed preferentially, indicating that adsorption efficiency depends on the number of functional groups of humic substances. Furthermore, the surface topography of the adsorbent was observed before and after adsorption by scanning electron microscopy. The calculated heat of adsorption was of 330 kJ mol(-1) which was evaluated from the Clapeyron-Clausius equation. Therefore, the adsorption type can be considered chemical. Since xonotlite can be easily synthesized and obtained at low cost, the adsorption method of humic and fulvic acids is superior to their precipitation.     

Fluorescence behaviour of Zn and Ni complexes of humic acids from different sources

Conventional fluorescence spectroscopy in the excitation, emission and synchronous scan modes and three-dimensional fluorescence spectroscopy in the form of an excitation-emission matrix (EEM) of fluorescence intensity as a function of excitation and emission wavelengths have been applied to the study of three humic acids (HAs) extracted from soil (SHA), peat (PHA) and compost (CHA) and their interaction products with Zn(II) and Ni(II) ions. Fluorescence spectra of HAs appear to be related to the nature and origin of the sample. A strong reduction of intensity of all peaks is observed in the spectra of HAs-metal complexes as compared to those of untreated HAs. Ni(II) exhibits greater quenching ability than Zn(II). Fluorescence quenching measured for complexes of HAs at increasing Ni(II) concentrations was linearly correlated with metal ion concentration. The different capacity to interact with metal ions showed by various HAs is attributed to their different molecular complexity.     

Sorption of U(VI) onto an artificial humic substance-kaolinite-associate

An artificial humic substance-kaolinite-associate (HSKA) was synthesized as a model substance for natural clays containing organic matter in clay formations, soils, and sediments. The U(VI) sorption onto this model substance was studied in batch experiments as a function of pH and compared to the U(VI) sorption onto kaolinite in absence and presence of separately added humic acid (HA). The HSKA has a TOC content of 4.9 mg g(-1). It was found that the humic matter associated with kaolinite exhibits an immobilizing as well as an mobilizing effect on U(VI). Between pH 3 and 5, humic matter causes an increase of the U(VI) sorption onto kaolinite, whereas at pH above 5 the release of humic matter from the associate into the solution and the formation of dissolved uranyl humate complexes reduces the U(VI) sorption. The U(VI) sorption onto the synthetic HSKA differs from that of U(VI) in the system U(VI)/HA/kaolinite with comparable amounts of separately added HA. Separately added HA causes a stronger mobilizing effect on U(VI) than humic matter present in HSKA. This can be attributed to structural and functional dissimilarities of the humic substances.     

Fractionation of heavy metals and distribution of organic carbon in two contaminated soils amended with humic acids

The effects of humic acids (HAs) extracted from two different organic materials on the distribution of heavy metals and on organic-C mineralisation in two contaminated soils were studied in incubation experiments. Humic acids isolated from a mature compost (HAC) and a commercial Spaghnum peat (HAP) were added to an acid soil (pH 3.4; 966 mg kg(-1) Zn and 9,229 mg kg(-1) Pb as main contaminants) and to a calcareous soil (pH 7.7; 2,602 mg kg(-1) Zn and 1,572 mg kg(-1) Pb as main contaminants) at a rate of 1.1g organic-C added per 100g soil. The mineralisation of organic-C was determined by the CO(2) released during the experiment. After 2, 8 and 28 weeks of incubation the heavy metals of the soils were fractionated by a sequential extraction procedure. After 28 weeks of incubation, the mineralisation of the organic-C added was rather low in the soils studied (<8% of TOC in the acid soil; <10% of TOC in the calcareous soil). Both humic acids caused significant Zn and Pb immobilisation (increased proportion of the residual fraction, extractable only with aqua regia) in the acid soil, while Cu and Fe were slightly mobilised (increased concentrations extractable with 0.1M CaCl(2) and/or 0.5M NaOH). In the calcareous soil there were lesser effects, and at the end of the experiment only the fraction mainly related to carbonates (EDTA-extractable) was significantly increased for Zn and decreased for Fe in the humic acids treated samples. However, HA-metal interactions provoked the flocculation of these substances, as suggested by the association of the humic acids with the sand fraction of the soil. These results indicate that humic acid-rich materials can be useful amendments for soil remediation involving stabilisation, although a concomitant slight mobilisation of Zn, Pb and Cu can be provoked in acid soils.