Al(III) and Fe(III) binding by humic substances in freshwaters, and implications for trace metal speciation

Published experimental data for Al(III) and Fe(III) binding by fulvic and humic acids can be explained approximately by the Humic Ion-Binding Model VI. The model is based on conventional equilibrium reactions involving protons, metal aquo ions and their first hydrolysis products, and binding sites ranging from abundant ones of low affinity, to rare ones of high affinity, common to all metals. The model can also account for laboratory competition data involving Al(III), Fe(III) and trace elements, supporting the assumption of common binding sites. Field speciation data (116 examples) for Al in acid-to-neutral waters can be accounted for, assuming that 60-70 % (depending upon competition by iron, and the chosen fulvic acid : humic acid ratio) of the dissolved organic carbon (DOC) is due to humic substances, the rest being considered inert with respect to ion binding. After adjustment of the model parameter characterizing binding affinity within acceptable limits, and with the assumption of equilibrium with a relatively soluble form of Fe(OH)₃, the model can simulate the results of studies of two freshwater samples, in which concentrations of organically complexed Fe were estimated by kinetic analysis.The model was used to examine the pH dependence of Al and Fe binding by dissolved organic matter (DOM) in freshwaters, by simulating the titration with Ca(OH)₂ of an initially acid solution, in equilibrium with solid-phase Al(OH)₃ and Fe(OH)₃. For the conditions considered, Al, which is present at higher free concentrations than Fe(III), competes significantly for the binding of Fe(III), whereas Fe(III) has little effect on Al binding. The principal form of Al simulated to be bound at low pH is Al³⁺, AlOH²⁺ being dominant at pH >6; the principal bound form of Fe(III) is FeOH²⁺ at all pH values in the range 4-9. Simulations suggest that, in freshwaters, both Al and Fe(III) compete significantly with trace metals (Cu, Zn) for binding by natural organic matter over a wide pH range (4-9). The competition effects are especially strong for a high-affinity trace metal such as Cu, present at low total concentrations (∼1 nM). As a result of these competition effects, high-affinity sites in humic matter may be less important for trace metal binding in the field than they are in laboratory systems involving humic matter that has been treated to remove associated metals.     

Sorption of Cu and Pb to kaolinite-fulvic acid colloids: Assessment of sorbent interactions

The sorption of Cu(II) and Pb(II) to kaolinite-fulvic acid colloids was investigated by potentiometric titrations. To assess the possible interactions between kaolinite and fulvic acid during metal sorption, experimental sorption isotherms were compared with predictions based on a linear additivity model (LAM). Suspensions of 5 g L⁻¹ kaolinite and 0.03 g L⁻¹ fulvic acid in 0.01 M NaNO₃ were titrated with Cu and Pb solutions, respectively. The suspension pH was kept constant at pH 4, 6, or 8. The free ion activities of Cu²⁺ and Pb²⁺ were monitored in the titration vessel using ion selective electrodes. Total dissolved concentrations of metals (by ICP-MS) and fulvic acid (by UV-absorption) were determined in samples taken after each titration step. The amounts of metals sorbed to the solid phase, comprised of kaolinite plus surface-bound fulvic acid, were calculated by difference. Compared to pure kaolinite, addition of fulvic acid to the clay strongly increased metal sorption to the solid phase. This effect was more pronounced at pH 4 and 6 than at pH 8, because more fulvic acid was sorbed to the kaolinite surface under acidic conditions. Addition of Pb enhanced the sorption of fulvic acid onto kaolinite at pH 6 and 8, but not at pH 4. Addition of Cu had no effect on the sorption of fulvic acid onto kaolinite. In the LAM, metal sorption to the kaolinite surface was predicted by a two-site, 1-pK basic Stern model and metal sorption to the fulvic acid was calculated with the NICA-Donnan model, respectively. The LAM provided good predictions of Cu sorption to the kaolinite-fulvic acid colloids over the entire range in pH and free Cu²⁺ ion activity (10⁻¹² to 10⁻⁵). The sorption of Pb was slightly underestimated by the LAM under most conditions. A fractionation of the fulvic acid during sorption to kaolinite was observed, but this could not explain the observed deviations of the LAM predictions from the experimental Pb sorption isotherms.     

Trace metal–humate interactions. I. Experimental determination of conditional stability constants

The enhancement of mobility of radionuclides in the geosphere through complexation by humic substances is a source of uncertainty in performance assessment of radioactive waste repositories. Only very few data sets are available which are relevant for performance assessment of an underground repository for radioactive waste. Using the equilibrium dialysis-ligand exchange method developed at the Paul Scherrer Institut, conditional stability constants for the formation of complexes of Aldrich humic acid with Ca²⁺, NpO₂⁺, Co²⁺, Ni²⁺, UO₂²⁺ and Eu³⁺ and complexes of Laurentian soil- and Suwannee River fulvic acid with Co²⁺, UO₂²⁺ and Eu³⁺ were measured. pH was varied between 5 and 10 and ionic strength between 0.02 and 0.2 M. The data are presented as equilibrium coefficients that are free from any model assumptions. The equilibrium coefficients increased in the order Ca²⁺≅NpO₂⁺<Co²⁺< Ni²⁺<UO₂²⁺< Eu³⁺. The quality of the data is assessed in an extended discussion of statistical and systematical errors, and by a critical ‘rereview’ of the auxiliary stability constants used for the calculation of the equilibrium coefficients. An approximate overall uncertainty of 0.5 log-units is estimated for the stability data reported. The conditional stability constants were found to increase markedly with increasing pH in the case of Co²⁺, UO₂²⁺ and Eu³⁺. For Ni²⁺, Ca²⁺ and NpO₂⁺ this effect was less pronounced. For all metal ions tested, the influence of ionic strength was of less importance, and the conditional stability constants did not show a significant dependence on the type of humic substances investigated.     

Speciation of rare earth elements in natural terrestrial waters: assessing the role of dissolved organic matter from the modeling approach

Humic Ion-Binding Model V, which focuses on metal complexation with humic and fulvic acids, was modified to assess the role of dissolved natural organic matter in the speciation of rare earth elements (REEs) in natural terrestrial waters. Intrinsic equilibrium constants for cation-proton exchange with humic substances (i.e., pK_MHA for type A sites, consisting mainly of carboxylic acids), required by the model for each REE, were initially estimated using linear free-energy relationships between the first hydrolysis constants and stability constants for REE metal complexation with lactic and acetic acid. pK_MHA values were further refined by comparison of calculated Model V “fits” to published data sets describing complexation of Eu, Tb, and Dy with humic substances. A subroutine that allows for the simultaneous evaluation of REE complexation with inorganic ligands (e.g., Cl⁻, F⁻, OH⁻, SO₄²⁻, CO₃²⁻, PO₄³⁻), incorporating recently determined stability constants for REE complexes with these ligands, was also linked to Model V. Humic Ion-Binding Model V’s ability to predict REE speciation with natural organic matter in natural waters was evaluated by comparing model results to “speciation” data determined previously with ultrafiltration techniques (i.e., organic acid-rich waters of the Nsimi-Zoetele catchment, Cameroon; dilute, circumneutral-pH waters of the Tamagawa River, Japan, and the Kalix River, northern Sweden). The model predictions compare well with the ultrafiltration studies, especially for the heavy REEs in circumneutral-pH river waters. Subsequent application of the model to world average river water predicts that organic matter complexes are the dominant form of dissolved REEs in bulk river waters draining the continents. Holding major solute, minor solute, and REE concentrations of world average river water constant while varying pH, the model suggests that organic matter complexes would dominate La, Eu, and Lu speciation within the pH ranges of 5.4 to 7.9, 4.8 to 7.3, and 4.9 to 6.9, respectively. For acidic waters, the model predicts that the free metal ion (Ln³⁺) and sulfate complexes (LnSO₄⁺) dominate, whereas in alkaline waters, carbonate complexes (LnCO₃⁺ + Ln[CO₃]₂⁻) are predicted to out-compete humic substances for dissolved REEs. Application of the modified Model V to a “model” groundwater suggests that natural organic matter complexes of REEs are insignificant. However, groundwaters with higher dissolved organic carbon concentrations than the “model” groundwater (i.e., >0.7 mg/L) would exhibit greater fractions of each REE complexed with organic matter. Sensitively analysis indicates that increasing ionic strength can weaken humate-REE interactions, and increasing the concentration of competitive cations such as Fe(III) and Al can lead to a decrease in the amount of REEs bound to dissolved organic matter.     

Groundwater quality on the territory of Kikinda municipality (Vojvodina,Serbia)

This paper provides insight into the quality of groundwater used for public water supply on the territory of Kikinda municipality (Vojvodina, Serbia) and main processes which control it. The following parameters were measured: color, turbidity, pH, KMnO₄ consumption, TDS, EC, NH₄ ⁺, Cl^?, NO₂ ^?, NO₃ ^?, Fe, Mn, total hardness, Ca²⁺, Mg²⁺, SO₄ ²⁺, HCO₃ ^?, K⁺, Na⁺, As. The correlations and ratios among parameters that define the chemical composition were determined aiming to identify main processes that control the formation of the chemical composition of the analyzed waters. Groundwater from 11 analyzed sources is Na–HCO₃ type. Intense color and elevated organic matter content of these waters originate from humic substances. The importance of organic matter decay is assumed by positive correlation between organic matter content and TDS, HCO₃ content. There is no evidence that groundwater chemistry is determined by the depth of captured aquifer interval. The main processes that control the chemistry of all analyzed water are cation exchange and feldspar weathering.     

Sorption of Ni on Na-rectorite studied by batch and spectroscopy methods

Sorption of Ni²⁺ on Na-rectorite as a function of contact time, temperature, pH and fulvic acid (FA)/humic acid (HA) was studied under ambient conditions. A pseudo-second-order rate equation was used to simulate the kinetic sorption. The removal of Ni²⁺ increased with increasing pH. The presence of FA/HA enhanced the sorption of Ni²⁺ at low pH values, whereas no drastic effect of FA/HA on Ni²⁺ uptake to rectorite was found at high pH values. The diffuse layer model (DLM) fitted the experimental data of Ni²⁺ sorption in the absence and presence of FA/HA very well with the aid of FITEQL 3.2. The Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models were used to simulate the sorption isotherms of Ni²⁺ at different temperatures. The thermodynamic data (ΔH⁰, ΔS⁰, ΔG⁰) were calculated from the temperature dependent sorption isotherms and the results suggested that the sorption process of Ni²⁺ on rectorite was spontaneous and endothermic. The sorption and species of Ni²⁺ on rectorite in the presence and absence of FA/HA was also investigated and characterized by XPS. The spectroscopic analysis indicated no drastic structural changes of Na-rectorite and the sorption of Ni²⁺ mainly occurred on the surface and at the edge position of Na-rectorite.     

Effects of humus on the environmental activity of mineral-bound Hg: Influence on Hg volatility

The effects of three humus fractions (fulvic acid, brown humic acid and grey humic acid) on the volatility of five types of mineral-bound Hg were investigated. Fulvic acid was found to strongly promote the volatilization of Hg bound by Fe₂O₃, MnO₂ and kaolinite, but suppressed the volatilization of Hg bound by bentonite and CaCO₃. Brown humic acid was found to enhance the volatilization of Hg bound from all the tested minerals, except for Fe₂O₃. Grey humic acid had the weakest effect in promoting or suppressing Hg volatilization. The influence of the various humus fractions on the volatilization of mineral-bound Hg is closely related to the complexing capacity and complex stability of the particular humus material. The higher the complexing capacity and the lower the complex stability, the more prominent is the humus material in promoting Hg volatility. The Hg sorption capacity and sorption strength of the minerals, as well as their Hg speciation characteristics, limit the effect that humus has to volatilize Hg.     

Comparison of binding abilities of fulvic and humic acids extracted from recent marine sediments with UO22+

Potentiometric titrations were used to measure conditional stability constants of UO₂²⁺-fulvic acid and UO₂²⁺-humic acid complexes. Both 2:1 and 1:1 COO^-:UO₂²⁺ binding were observed. With decreasing metal concentration (2.5·10⁻⁴-6.25·10⁻⁵ M) increasing amounts of UO₂²⁺ were in the form of 1:1 humate complexes and 2:1 fulvate complexes. Despite the high nitrogen content and the low acidic OH group content, the successive stability constant values were similar to those determined for divalent cations associated with fulvic and humic compounds isolated from soils. Stability constant values increase simultaneously with increasing ionization of the humic (or fulvic) acid polyelectrolytes and with decreasing metal concentration.     

The adsorption of aquatic humic substances by iron oxides

The interactions of humic substances from Esthwaite Water with hydrous iron oxides (α-FeOOH, α-Fe₂O₃, amorphous Fe-gel) have been examined by measuring adsorption isotherms and by microelectrophoresis. In Na⁺-Cl^?-HCO₃^?at I = 0.002 M (medium I) the extent of adsorption decreases with increasing pH. The results are consistent with a mechanism involving ligand exchange of humic anionic groups with H₂O and OH^?of surface Fe-OH₂⁺and Fe-OH groups respectively, with an increasing degree of protonation of the adsorbed humics as the adsorption density increases at constant pH.At pH 7 in a medium containing Mg²⁺, Ca²⁺ and SO₄^2?, at their Esthwaite Water concentrations and at I= 0.002 M (medium II) the adsorption capacity of goethite (α-FeOOH) is approximately twice that in medium I. Electrophoresis experiments show that the extra capacity is associated with coadsorption of Mg²⁺ and/or Ca²⁺ ions.When the iron oxides are added to samples of Esthwaite Water itself they become negatively charged and plots of electrophoretic mobility against pH for the natural water are identical to those in medium II plus humics.     

Comparison of binding abilities of fulvic and humic acids extracted from recent marine sediments with UO2

Potentiometric titrations were used to measure conditional stability constants of UO₂²⁺-fulvic acid and UO₂²⁺-humic acid complexes. Both 2:1 and 1:1 COO^-:UO₂²⁺ binding were observed. With decreasing metal concentration (2.5·10⁻⁴-6.25·10⁻⁵ M) increasing amounts of UO₂²⁺ were in the form of 1:1 humate complexes and 2:1 fulvate complexes. Despite the high nitrogen content and the low acidic OH group content, the successive stability constant values were similar to those determined for divalent cations associated with fulvic and humic compounds isolated from soils. Stability constant values increase simultaneously with increasing ionization of the humic (or fulvic) acid polyelectrolytes and with decreasing metal concentration.     

On the model of Mn,Fe, Ni,Co ore formation in recent basins: Experiments with the synthesis of Me-hydroxide phases on Mn3O4

Experiments on the sorption of dissolved Ni, Co, Mn, Fe from seawater by Mn₃O₄ reveal a sequence of reactions taking place: Ion exchange, hydrolysis, then autocatalytic oxidation and layer formation on the interface. The composition of the new compounds depends on the kinetics of i) sorption, and ii) interface oxidation. The highest oxidized Me ions accumulate at low sorption rates, i. e. when sorption does not inhibit interface oxidation: 60% Mn⁴⁺, 30% Ni³⁺ & 30% Co³⁺ are a representative example for that layer type. Iron is present in this layer as amorphous FeOOH·xH₂O according to Mössbauer spectra. Specific for the Me sorption by Mn₃O₄ is the interaction of Ni & Co with Mn²⁺ and Mn³⁺ of the sorbent lattice. Mn is found in the solute phase equivalent to 16, 14% of the adsorbed Co or 17, 96% of the adsorbed Ni. These results confirm the earlier presented model on the transition metal accumulation in recent basins as taking place in distinct stages with interface autocatalysis for the Me oxidation playing the main role.     

Retention of fly ash-derived copper in sediments of the Pandu River near Kanpur,India

A coal-based thermal power plant is situated on the bank of the Pandu River, which is a tributary to the Ganges near Kanpur. River sediments downstream from the ash pond outfall are contaminated by fly ash. In order to establish the role of soils and sediments in retaining fly ash-derived heavy metals, copper was investigated as a model metal. A maximum concentration of 70 ppm Cu could be leached from the fly ash, confirming that it is a major source of this metal. Soil samples and river sediments were examined for Cu adsorption in the natural state as well as after treatment with H₂O₂, EDTA, and H₂O₂ followed by EDTA. The organic fraction of the samples was determined, and it had a major control on removal of Cu from a solution with 10^–4 M initial concentration. Further characterization of organic matter indicated that with reference to natural samples, the humic acid fraction had a copper enrichment factor in the range 9.1–15.1. The factor for fulvic acids, in contrast, was between 3.5 and 5.5. This leads to the conclusion that river deposits rich in humic acids would withstand relatively high metal loads. Only when the metal input exceeds the maximum retention potential, would the metal be fractionated into the aqueous phase and act as a potential biocide.     

Non-Stoichiometric magnesian spinels in shale xenoliths from a native iron-bearing andesite at Asuk,Disko, central West Greenland

A strongly reduced native iron-bearing andesite breccia from Disko contains graphite-rich modified shale xenoliths with magnesian spinels. These spinels are free from or very poor in ferric iron and vary considerably within the MgO-FeO-Cr₂O₃-Al₂O₃ compositional space. Through a simple substitution of the type 3 (Mg, Fe)²⁺ ⇆ 2(Al, Cr)³⁺+□_vacancy, the spinels vary from stoichiometric (Mg, Fe)²⁺ (Al, Cr)³⁺ ₂O₄ towards (Al, Cr)₂O₃. The simple substitution of Cr for Al suggests that Cr was accepted into the spinel structure as Cr³⁺, despite the reduced nature of the enclosing andesite. The most magnesian spinels are cation deficient spinel_ss in the synthetic systems MgO-Al₂O₃ and MgO-Al₂O₃-Cr₂O₃. The absence of exolved (Al, Cr)₂O₃-component is probable due to rapid quenching.     

Sorption of Eu(III)/Cm(III) on Ca-montmorillonite and Na-illite. Part 2: Surface complexation modelling

Sorption edges and isotherms for Eu(III) uptake on Ca-montmorillonite and Na-illite in 0.066 mol/L Ca(ClO₄)₂ and 0.1 mol/L NaClO₄ background electrolytes, respectively, were modelled using a quasi-mechanistic sorption model (the two site protolysis non electrostatic surface complexation and cation exchange (2SPNE SC/CE) model). For both clay minerals the Eu sorption edges could be quantitatively modelled in the pH range ∼3 to ∼10 using cation exchange reactions for Eu³⁺/Na⁺ and Eu³⁺/Ca²⁺ and three surface complexation reactions on the strong sorption sites forming ≡S^SOEu²⁺, ≡S^SOEuOH⁺ and ≡S^SOEu(OH)₂° inner sphere complexes which appear successively with increasing pH. Time resolved laser fluorescence spectroscopy (TRLFS) measurements of Cm(III) loaded Ca-montmorillonite and Na-illite were available from Part 1 of this work. De-convolution of the normalised fluorescence spectra measured at different pH values indicated three distinct Cm surface complexes, Cm complexes 1, 2 and 3 for both clay minerals, in agreement with model predictions, but with different distribution functions for the individual species. Under the assumption that Eu and Cm exhibit essentially the same hydrolysis and sorption behaviour, the Eu surface complexation constants were used to predict surface species distribution functions for Cm under the same experimental conditions used in the TRLFS measurements. Comparison of modelled and experimentally deduced species distributions indicated that for both clay minerals peak heights and widths of the three peaks did not correspond particularly well. It is shown that the calculated species distribution functions are sensitive to the values of the hydrolysis constants used in the calculations, whereas modelling the sorption edge measurements by applying the 2SPNE SC/CE approach is much less sensitive. By modifying the values of the hydrolysis constants within their uncertainty range and re-modelling the sorption edges, considerably better correspondence between the modelled and TRLFS species distribution functions was found. In particular, peak positions, heights and widths for the model predicted peaks for the ≡S^SOCm²⁺ and ≡S^SOCmOH⁺ species distribution, and those for Cm complexes 1 and 2 derived from TRLFS, were found to be very close for both clay minerals. However, discrepancies were still apparent between the profile for the calculated ≡S^SOEu(OH)₂° surface species and the Cm complex 3 species, especially in the case of Na-illite.     

Kinetics of brucite dissolution at 25°C in the presence of organic and inorganic ligands and divalent metals

Brucite (Mg(OH)₂) dissolution rate was measured at 25°C in a mixed-flow reactor at various pH (5 to 11) and ionic strengths (0.01 to 0.03 M) as a function of the concentration of 15 organic and 5 inorganic ligands and 8 divalent metals. At neutral and weakly alkaline pH, the dissolution is promoted by the addition of the following ligands ranked by decreasing effectiveness: EDTA ≥ H₂PO₄⁻ > catechol ≥ HCO₃⁻ > ascorbate > citrate > oxalate > acetate ∼ lactate and it is inhibited by boric acid. At pH >10.5, it decreases in the presence of PO₄³⁻, CO₃²⁻, F⁻, oxine, salicylate, lactate, acetate, 4-hydroxybenzoate, SO₄²⁻ and B(OH)₄⁻ with orthophosphate and borate being the strongest and the weakest inhibitor, respectively. Xylose (up to 0.1 M), glycine (up to 0.05 M), formate (up to 0.3 M) and fulvic and humic acids (up to 40 mg/L DOC) have no effect on brucite dissolution kinetics. Fluorine inhibits dissolution both in neutral and alkaline solutions. From F sorption experiments in batch and flow-through reactors and the analysis of reacted surfaces using X-ray Photoelectron Spectroscopy (XPS), it is shown that fluorine adsorption is followed by its incorporation in brucite lattice likely via isomorphic substitution with OH. The effect of eight divalent metals (Sr, Ba, Ca, Pb, Mn, Fe, Co and Ni) studied at pH 4.9 and 0.01 M concentration revealed brucite dissolution rates to be correlated with the water molecule exchange rates in the first hydration sphere of the corresponding cation.The effect of investigated ligands on brucite dissolution rate can be modelled within the framework of the surface coordination approach taking into account the adsorption of ligands on dissolution-active sites and the molecular structure of the surface complexes they form. The higher the value of the ligand sorption constant, the stronger will be its catalyzing or inhibiting effect. As for Fe and Al oxides, bi- or multidentate mononuclear surface complexes, that labilize Mg-O bonds and water coordination to Mg atoms at the surface, enhance brucite dissolution whereas bi- or polynuclear surface complexes tend to inhibit dissolution by bridging two or more metal centers and extending the cross-linking at the solid surface. Overall, results of this study demonstrate that very high concentrations of organic ligands (0.01-0.1 M) are necessary to enhance or inhibit brucite dissolution. As a result, the effect of extracellular organic products on the weathering rate of Mg-bearing minerals is expected to be weak.     

Chemistry of metal–humic complexes contained in Megalopolis lignite and potential application in modern organomineral fertilization

Lignite samples from two deposits located in the Megalopolis Basin, Southern Greece, were evaluated for their potential applicability as raw materials for the production of organomineral fertilizers. Fundamental chemical analyses were carried out to demonstrate high humic substances and metal contents. To determine their relative distribution in the Megalopolis lignite extract, eight elements, namely Na, K, Cd, Mn, Mg, Pb, Zn, and Cu, were studied both in H₂O and in Na₄P₂O₇/NaOH solutions. The behavior of these metals showed significant variations; Zn, Pb, Cd, and Cu associate mostly to the humic substances and proved scarce in the water extract. Contrarily, K and Mg gave a significantly low total yield in the Na₄P₂O₇/NaOH solution, while Mn was classified among the least extracted elements. Further enrichment of Megalopolis humic substances in these metals was achieved; Pb and Mg proved the most and least retained metal, respectively. Decomplexation titration curves of humic matter saturated with these metal ions demonstrated that novel organomineral fertilizing materials may develop based on optimized metal ion and humate contents, which can retain metals in a soluble form within a wide pH range. Formation of complexes between humic substances and Zn, Cd, and Mg was clearly indicated.     

Sources of sedimentary humic substances: vascular plant debris

A modern Washington continental shelf sediment was fractionated densimetrically using either an organic solvent, CBrCl₃, or aqueous ZnCl₂. The resulting low density materials (<2.06 g/ml) account for only 1% of the sediment mass but contain 25% of the sedimentary organic carbon and 53% of the lignin. The C/N ratios (30–40) and lignin phenol yields ($\text{Λ = 8}$) and compositions indicate that the low density materials are essentially pure vascular plant debris which is slightly enriched in woody (versus nonwoody) tissues compared to the bulk sediment. The low density materials yield approximately one-third of their organic carbon as humic substances and contribute 23% and 14% of the total sedimentary humic and fulvic acids, respectively. Assuming that the lignin remaining in the sedimentary fraction is also contained in plant fragments that yield similar levels of humic substances, then 50% and 30% of the total humic and fulvic acids, respectively, arise directly from plant debris.Base-extraction of fresh and naturally degraded vascular plant materials reveals that significant levels of humic and fulvic acids are obtained using classical extraction techniques. Approximately 1–2% of the carbon from fresh woods and 10–25% from leaves and bark were isolated as humic acids and 2–4 times those levels as fulvic acids. A highly degraded hardwood yielded up to 44% of its carbon as humic and fulvic acids. The humic acids from fresh plants are generally enriched in lignin components relative to carbohydrates and recognizable biochemicals account for up to 50% of the total carbon. Humic and fulvic acids extracted directly from sedimentary plant debris could be responsible for a major fraction of the biochemical component of humic substances.     

Aggregation of aquatic humic substances

Humic substances (HS) were isolated from Penwhirn Reservoir (PR) and Esthwaite Water (EW) and their removal from solution by centrifugation was studied as a function of pH, humic concentration and molecular weight, and CaCl₂ concentration. Large amounts (up to 50%) of PR HS could be removed but only small amounts (? 3%) of EW HS. At pH ? 5 removal of PR HS by Ca²⁺ can be explained satisfactorily in terms of decreases in humic solubilities induced by complexation with the cation. However, removal induced by protonation of the PR HS is unusual in that it decreases with increasing humic concentration.The results suggest that PR HS comprise a range of molecules differing in solubility, with the high-molecular-weight (40,000) components being the least soluble. The EW HS consist of molecules of weight-average molecular weight 5000 and resemble similarly sized PR HS in that they remain unaggregated in solution even when highly complexed with Ca²⁺.     

Geochemical reactions and dynamics during titration of a contaminated groundwater with high uranium, aluminum, and calcium

This study investigated possible geochemical reactions during titration of a contaminated groundwater with a low pH but high concentrations of aluminum, calcium, magnesium, manganese, and trace contaminant metals/radionuclides such as uranium, technetium, nickel, and cobalt. Both Na-carbonate and hydroxide were used as titrants, and a geochemical equilibrium reaction path model was employed to predict aqueous species and mineral precipitation during titration. Although the model appeared to be adequate to describe the concentration profiles of some metal cations, solution pH, and mineral precipitates, it failed to describe the concentrations of U during titration and its precipitation. Most U (as uranyl, UO₂²⁺) as well as Tc (as pertechnetate, TcO₄⁻) were found to be sorbed and coprecipitated with amorphous Al and Fe oxyhydroxides at pH below ∼5.5, but slow desorption or dissolution of U and Tc occurred at higher pH values when Na₂CO₃ was used as the titrant. In general, the precipitation of major cationic species followed the order of Fe(OH)₃ and/or FeCo_0.1(OH)_3.2, Al₄(OH)₁₀SO₄, MnCO₃, CaCO₃, conversion of Al₄(OH)₁₀SO₄ to Al(OH)_3,am, Mn(OH)₂, Mg(OH)₂, MgCO₃, and Ca(OH)₂. The formation of mixed or double hydroxide phases of Ni and Co with Al and Fe oxyhydroxides was thought to be responsible for the removal of Ni and Co in solution. Results of this study indicate that, although the hydrolysis and precipitation of a single cation are known, complex reactions such as sorption/desorption, coprecipitation of mixed mineral phases, and their dissolution could occur simultaneously. These processes as well as the kinetic constraints must be considered in the design of the remediation strategies and modeling to better predict the activities of various metal species and solid precipitates during pre- and post-groundwater treatment practices.