Field experiments yield new insights into gas exchange and excess air formation in natural porous media

Gas exchange between seepage water and soil air within the unsaturated and quasi-saturated zones is fundamentally different from gas exchange between water and gas across a free boundary layer, e.g., in lakes or rivers. In addition to the atmospheric equilibrium fraction, most groundwater samples contain an excess of dissolved atmospheric gases which is called “excess air”. Excess air in groundwater is not only of crucial importance for the interpretation of gaseous environmental tracer data, but also for other aspects of groundwater hydrology, e.g., for oxygen availability in bio-remediation and in connection with changes in transport dynamics caused by the presence of entrapped air bubbles. Whereas atmospheric solubility equilibrium is controlled mainly by local soil temperature, the excess air component is characterized by the (hydrostatic) pressure acting on entrapped air bubbles within the quasi-saturated zone. Here we present the results of preliminary field experiments in which we investigated gas exchange and excess air formation in natural porous media. The experimental data suggest that the formation of excess air depends significantly on soil properties and on infiltration mechanisms. Excess air was produced by the partial dissolution of entrapped air bubbles during a sprinkling experiment in fine-grained sediments, whereas similar experiments conducted in coarse sand and gravel did not lead to the formation of excess air in the infiltrating water. Furthermore, the experiments revealed that the noble gas temperatures determined from noble gases dissolved in seepage water at different depths are identical to the corresponding in situ soil temperatures. This finding is important for all applications of noble gases as a paleotemperature indicator in groundwater since these applications are always based on the assumption that the noble gas temperature is identical to the (past) soil temperature.     

Experimental investigations on the formation of excess air in quasi-saturated porous media

The formation of an excess of dissolved gas (“excess air”) in quasi-saturated media was studied by analyzing and interpreting dissolved noble gas concentrations in laboratory column experiments. Using quartz sand filled columns of 1 m length, two different experimental designs were realized. In the first, groundwater recharge was simulated by a unidirectional vertical water flow through the columns. In the second, groundwater level fluctuations in an aquifer zone without active infiltration were reproduced by cyclic water level fluctuations in the columns. The reproducible generation of excess air under these defined, near natural conditions was successful. Partial or complete dissolution of air bubbles entrapped in the quartz sand could be identified as the mechanism responsible for the generation of excess air. Depending on the experimental design, supersaturation of the dissolved atmospheric noble gases ranging between 1.4% ΔNe and 16.2% ΔNe was found. The measured noble gas patterns were interpreted using inverse modeling and conceptual gas exchange models and were compared to results of numerical simulations of gas bubble dissolution in water filled soil columns. The gas composition in most of the samples resembles either unfractionated pure atmospheric excess air or is fractionated in accordance with closed-system equilibration between entrapped air and surrounding water. In addition to the amount of entrapped air, the hydrostatic pressure exerted on the entrapped air bubbles is the dominating parameter responsible for the total amount of dissolved air. The composition of the excess air component is controlled by the water flow regime, the bubble size distribution, the initially dissolved gas concentrations and the initially entrapped gas composition.     

Sorption of silica by clay minerals

Clay minerals were reacted with silica-spiked solutions of unbuffered distilled water; water buffered at pH 5.5, 8 and 10; alkali chloride solutions; natural and artificial sea water to assess the influence of pH, silica and cation activities. The data are plotted as silica produced by dissolution or sorption of silica by clay surface as a function of initial silica concentration at a given pH and solution composition. This allows the determination of the dissolved silica value at which the clay mineral surface neither dissolves nor sorbs silica. The values of the various activities in different solutions are used to infer the phase equilibria between solution, clay mineral and the surface phase produced either by dissolution or sorption. Most intensively investigated were sorption reactions of kaolinite in sea water and other ionic solutions to form silica-rich, cation-rich surface phases in cationic solutions and silica-rich phases in cation-free solutions.Inferred equilibrium constants imply that silicate reconstitution is doubtful as a mechanism for partial control of silica and cation composition of sea water but is reasonable in silica-rich interstitial waters.     

Effects of pretreatment and aging on chromite flotation

Anionic and cationic flotation of a Stillwater Complex chromite was studied as a function of pH and various pretreatments of the mineral. Aging the ground mineral in air markedly decreased anionic (sodium dodecylsulfate) flotation below pH3 and enhanced it above pH 4–5. Such aging increased cationic (dodecylammonium chloride) flotation in the basic pH region. Mildly preheating the mineral enhanced anionic flotation. Increased conditioning time in collector solution decreased anionic flotation. Strongly acid pretreating the mineral caused it to behave like a simple charged oxide toward both anionic and cationic flotation. These phenomena appear to be related to the effect of aging on the amounts of Fe(II) and Fe(III), of Cr(III) and Cr(VI) and of Mg(II) on the mineral's surface.     

Poroelastic behaviour of fine compacted soils in the unsaturated to saturated transition zone

The behaviour of quasi-saturated materials is important to consider when designing cuttings and embankments in which earthwork materials are compacted to the optimum proctor density. Under this condition, the in-pore gaseous phase takes the form of air pockets and bubbles embedded within the liquid phase, which significantly affects the overall behaviour of the soil. The assessment of highly saturated soils thus requires a precise understanding of hydro-chemo-mechanical couplings between the entrapped air, the in-pore liquid and the solid skeleton. This paper presents a fully coupled poromechanical model that separates the kinematics and the mechanical behaviours of the phases in their interactions with each other (e.g., liquid water, dissolved air, gaseous air and solid matrix). The assumptions about the entrapped air behaviour are defined from a bibliographic study, and linear elastic behaviour is used for both the liquid phase and the solid skeleton. The model is implemented in the FEM code COMSOL and is subsequently used to simulate oedometric tests under different loading paths: undrained compression or imposed liquid pressure variation at constant stress. The behaviour, which shows a continuous transition from unsaturated to saturated, is logical and consistent with available experimental data.     

Precipitate flotation of copper as the sulfide,using recyclable amphoteric surfactants

An experimental study was made to identify surfactants which are effective for removal of copper from dilute aqueous solution (100–500 ppm) by precipitate flotation as the sulfide, and which at the same time can be recovered from the CuS product for recycle. Batch flotation experiments confirmed that a cationic surfactant was necessary for flotation of CuS from such dilute suspensions; however, no satisfactory way could be found for recovering cationic surfactants from the CuS. This led to consideration of amphoteric surfactants, which are cationic at low pH and anionic at high pH. It was found that a change to negative, rather than simply neutral, charge was required for efficient surfactant recovery. It was further found, through the assistance of experiments in which the CuS suspension was agitated with solvents, that certain functional groups which interact chemically with the CuS surface should also be absent from the surfactant molecule. Following this logic, Amphoterge K-2 (Lonza Chemical Co.) was identified as a suitable surfactant, provided CuS was precipitated with S^2? in excess. Tests established that 95% of adsorbed Amphoterge K-2 could be recovered by raising the pH to 11 and boiling the suspension for one hour, followed by decanting. Surfactant thus recovered was effective in a second flotation test. Foamate solids settled rapidly; such behavior would help reduce the consumption of chemicals for the pH change.Column flotation studies were made using Amphoterge K-2 for removal of Cu²⁺ present at 100 ppm and pH = 2. High removals of CuS could be obtained at concentrations of surfactant above about 25 ppm, for which conditions a substantial fraction of the surfactant remains in solution rather than being adsorbed onto the CuS. The recovery of CuS would be improved by introducing the surfactant in a separate feed, below the feed of CuS suspension. Adding some surfactant in the CuS feed, as well as in a lower feed, gave an even better recovery of CuS (99.8%) at sufficiently high surfactant loadings.     

Evaluation of slurry settling rate using fuzzy rule-based modeling

The pressure acid leach process is the most widely used method of metal extraction from laterite ores. The self-weight settling rate of the ore slurries governs the throughput of the process and is improved by adding synthetic polymers. The charge density, molecular weight, and dosage of the polymers are the key factors influencing the settling rate of the slurries. This interdisciplinary paper uses the geotechnical understanding of hindered sedimentation for a mining engineering application. A conceptual fuzzy rule-based model was developed to evaluate the initial hydraulic conductivity of polymer-modified laterite ore slurries. Identification of control parameters and selection of the model architecture (fuzzy rule-base) were based on expert judgment. The developed model was trained and validated using bench-scale settling test data. The model reasonably predicts the initial hydraulic conductivity of polymer-added laterite ore slurry with a coefficient of determination of 0.75. Rank correlation coefficient-based sensitivity analyses indicated that charge density was the most significant polymer parameter followed by molecular weight and then by dosage. Charge density accounted for more than 97% of variability in the initial hydraulic conductivity estimates for both anionic and cationic polymers.     

Kinetics of Fe(III) precipitation in aqueous solutions at pH 6.0-9.5 and 25 °C

The kinetics of Fe(III) precipitation in synthetic buffered waters have been investigated over the pH range 6.0-9.5 using a combination of visible spectrophotometry, ⁵⁵Fe radiometry combined with ion-pair solvent extraction of chelated iron and numerical modeling. The rate of precipitation, which is first order with respect to both dissolved and total inorganic ferric species, varies by nearly two orders of magnitude with a maximum rate constant of 16 ± 1.5 × 10⁶ M⁻¹ s⁻¹ at a pH of around 8.0. Our results support the existence of the dissolved neutral species, Fe(OH)₃⁰, and suggest that it is the dominant precursor in Fe(III) polymerization and subsequent precipitation at circumneutral pH. The intrinsic rate constant of precipitation of Fe(OH)₃⁰ was calculated to be allowing us to predict rates of Fe(III) precipitation in the pH range 6.0-9.5. The value of this rate constant, and the variation in the precipitation rate constant over the pH range considered, are consistent with a mechanism in which the kinetics of iron precipitation are controlled by rates of water exchange in dissolved iron hydrolysis species.     

The hydrolysis of gold(I) in aqueous solutions to 600°c and 1500 bar

The solubility of gold has been measured in aqueous solutions at temperatures between 300 and 600°C and pressures from 500 to 1500 bar to determine the stability and stoichiometry of the hydroxy complexes of gold(I) in hydrothermal solutions. The experiments were carried out using a flow-through autoclave system. The solubilities, measured as total dissolved gold, were in the range 1.2 × 10⁻⁸ to 2.0 × 10⁻⁶ mol kg⁻¹ (0.002 to 0.40 mg kg⁻¹), in solutions of total dissolved sodium between 0.0 and 0.5 mol kg⁻¹, and total dissolved hydrogen between 4.0 × 10⁻⁶ and 4.0 × 10⁻⁴ mol kg⁻¹. At constant hydrogen molality, the solubility of gold increases with increasing temperature and decreases with increasing pressure. The solubilities were found to be independent of pH but increased with decreasing hydrogen molality at constant temperature and pressure. Consequently, gold dissolves in aqueous solutions of acidic to alkaline pH according to the reactionAu(s)+H₂O(l)=AuOH(aq)+0.5H₂(g) K_s,1The solubility constant, logK_s,1, increases with increasing temperature from a minimum of −8.76 (±0.18) at 300°C and 500 bar to a maximum of −7.50 (±0.11) at 500°C and 1500 bar and decreases to −7.61 (±0.08) at 600°C and 1500 bar. From the equilibrium solubility constant and the redox potential of gold, the formation constant to form AuOH(aq) was calculated. At 25°C the complex formation is characterised by an exothermic enthalpy and a positive entropy. With increasing temperature and decreasing pressure, the formation reaction becomes endothermic and is accompanied by a large positive entropy, indicating a greater electrostatic interaction between Au⁺ and OH⁻.     

Selective flotation of phosphatic ores having a siliceous and/or a carbonated gangue

As a result of the numerous studies carried out on assorted phosphate deposits by various methods, a new technique has been developed in the laboratory for the differential flotation of phosphates, especially sedimentary ones, with the aid of collectors which are amphoteric, i.e. they simultaneously possess a cationic and an anionic function, according to the working pH.This type of collector is already used industrially: for instance, an N-sarcosin is used at Siilinjärvi (Finland) based on an Hellsten and Klingberg patent (1978). This installation was described by Kiukkola (1980) and Anonymous (1982). However, only the anionic pole was used in the direct flotation of igneous apatite.This method has been applied to many types of sedimentary deposit. In view of the encouraging preliminary results, a patent has been lodged by Blazy et al. (1981) and this article will attempt, as far as possible, to compare the results obtained with those previously acquired, either in our own laboratories or in other centers.     

废泥浆脱水的试验研究

岩土工程施工产生的废泥浆含水量高,脱水性差,因此如何提高废泥浆的脱水量至关重要。试验中通过对废泥浆的物理化学调质,以改变废泥浆颗粒表面物化性质和组分,破坏废泥浆的胶体结构,减小与水的亲和力,从而改善废泥浆的脱水性能。对不同种类的无机材料和有机高分子絮凝材料的试验分析发现,有机高分子聚丙烯酰胺PAM的絮凝脱水效果要优于无机材料。在阳离子型PAM、阴离子型PAM、非离子型PAM三类材料对废泥浆的絮凝脱水效果中,阳离子型PAM的絮凝脱水效果最好。     

边坡虹吸排水管内空气积累原因及应对措施

坡体地下水位上升是诱发滑坡的重要因素,实时排出地下水是防治边坡地质灾害的有效手段。虹吸排水具有免动力和流动过程由液位变化自动控制的物理特性,可满足实时排出坡体地下水的需要,但虹吸管中空气积累会导致虹吸过程中断,制约了边坡虹吸排水技术的推广应用。溶解于水的空气因虹吸管内压力降低而释出是形成气泡的物理基础。实验结果表明,虹吸进水口水面以上垂直高度3.5 m以上就会出现大量气泡,经过虹吸顶点后,气泡发生强烈的兼并形成大气泡。当虹吸管的进出水口的水头差较大时,气泡间的水弹容易推动气泡从出水口排出。当虹吸管直径大于5 mm时,缓慢的虹吸流动,会发生管内气泡的积累,最终破坏虹吸过程;虹吸管的直径小于4 mm时,可以形成基本稳定的弹状流。因此,为保持边坡虹吸过程长期有效,经常性降雨并且坡体地下水丰富的地区可选用直径为5 mm的虹吸管,非经常性降雨的地区应选择小于等于4 mm的虹吸管。     

The emergence of life from iron monosulphide bubbles at a submarine hydrothermal redox and pH front

Here we argue that life emerged on Earth from a redox and pH front at c. 4.2 Ga. This front occurred where hot (c. 150 degrees C), extremely reduced, alkaline, bisulphide-bearing, submarine seepage waters interfaced with the acid, warm (c. 90 degrees C), iron-hearing Hadean ocean. The low pH of the ocean was imparted by the ten bars of CO2 considered to dominate the Hadean atmosphere/hydrosphere. Disequilibrium between the two solutions was maintained by the spontaneous precipitation of a colloidal FeS membrane. Iron monosulphide bubbles comprising this membrane were inflated by the hydrothermal solution upon sulphide mounds at the seepage sites. Our hypothesis is that the FeS membrane, laced with nickel, acted as a semipermeable catalytic boundary between the two fluids, encouraging synthesis of organic anions by hydrogenation and carboxylation of hydrothermal organic primers. The ocean provided carbonate, phosphate, iron, nickel and protons; the hydrothermal solution was the source of ammonia, acetate, HS-, H2 and tungsten, as well as minor concentrations of organic sulphides and perhaps cyanide and acetaldehyde. The mean redox potential (delta Eh) across the membrane, with the energy to drive synthesis, would have approximated to 300 millivolts. The generation of organic anions would have led to an increase in osmotic pressure within the FeS bubbles. Thus osmotic pressure could take over from hydraulic pressure as the driving force for distension, budding and reproduction of the bubbles. Condensation of the organic molecules to polymers, particularly organic sulphides, was driven by pyrophosphate hydrolysis. Regeneration of pyrophosphate from the monophosphate in the membrane was facilitated by protons contributed from the Hadean ocean. This was the first use by a metabolizing system of protonmotive force (driven by natural delta pH) which also would have amounted to c. 300 millivolts. Protonmotive force is the universal energy transduction mechanism of life. Taken together with the redox potential across the membrane, the total electrochemical and chemical energy available for protometabolism amounted to a continuous supply at more than half a volt. The role of the iron sulphide membrane in keeping the two solutions separated was appropriated by the newly synthesized organic sulphide polymers. This organic take-over of the membrane material led to the miniaturization of the metabolizing system. Information systems to govern replication could have developed penecontemporaneously in this same milieu. But iron, sulphur and phosphate, inorganic components of earliest life, continued to be involved in metabolism.     

Sonochemical degradation of endocrine disrupting chemicals 17β-estradiol and 17α-ethinylestradiol in water and wastewater

The sonochemical degradation of 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) in water and wastewater was investigated at ultrasonic frequency of 850 kHz. The effects of pH, initial concentrations, temperature, power and dissolved organic carbon were examined. The results obtained indicated that the rate of ultrasonic degradation of E2 and EE2 in water and wastewater is influenced by the pH, power, air sparging and the dissolved organic content of the aqueous solutions. Mass degradation rates of E2 and EE2 per kW ranged from 1.7 to 4.0 mg kW^?1 at varying process parameters. The degradation process followed the pseudo-second-order kinetic model with rate constant of 1.71 × 10^?2 min^?1 at 25 °C. The value for activation energy (E _a = 15.21 kJ mol^?1) obtained from Arrhenius-type plot, indicated that the ultrasonic degradation of steroid hormones is thermodynamically feasible, and does not progress only on radical reactions but other intermediate reaction processes. In wastewater, the higher dissolved organic carbon significantly reduced the effectiveness of degradation of the E2 and EE2 showing that ultrasound treatment will be more effective as a tertiary treatment option in wastewater applications.     

Humic acids coagulation: influence of divalent cations

The effects of the ionic strength (maintained by LiCl, NaCl or KCl) and Ca²⁺ and Mg²⁺ concentration on the coagulation of purified humic acids (HA) was studied. Solutions of known ionic strengths, pcH, Ca²⁺ and Mg²⁺ concentrations were prepared with HA and filtered to obtain the fraction with a size smaller than 100 kD. After a 50 day storage, samples of these solutions were filtered again (100 kD) and the total organic C (TOC) of the filtered solutions measured. The HA coagulation increased with salt concentration, with the cationic charge, and for cations of the same charge, with the cationic charge density. The coagulation decreased for pcH values of 4 to 7–8 in the absence of and presence of Mg²⁺ and Ca²⁺. In the absence of the divalent cations, the coagulation has a constant value for pcH>8, but, in the presence of Mg²⁺ and Ca²⁺, increases at pcH values greater than 9. The coagulation of humic materials occurs whether the samples are exposed to light or kept in the dark, although the coagulation kinetics are slower for the samples kept in the dark. The size distribution of size-fractionated humic solutions changes over time to a size distribution similar to that of the original humic solution before it was size-fractionated. The results are explained by the DLVO theory.     

水气混合洞塞泄流溶解氧输移扩散的数值计算

为研究水气二相混合洞塞泄流欠饱和溶解氧输移扩散行为特性,揭示气体体积分数、进口溶解氧浓度、雷诺数等流动特征参数和洞塞尺寸等几何参数对溶解氧浓度恢复的影响规律,开展了水气二相混合洞塞泄流溶解氧输移扩散的室内模型试验,观测流速、压力和溶解氧浓度分布。建立了水气二相混合洞塞泄流溶解氧输移扩散数学模型,并利用物理模型试验数据对数学模型进行了验证。利用验证后的数学模型,分别计算不同进口气体体积分数、溶解氧浓度、雷诺数、洞塞长度和洞塞直径条件下水气二相混合洞塞泄流溶解氧浓度恢复情况。结果发现:气体体积分数越大,进口溶解氧浓度与饱和溶解氧浓度差值越大,雷诺数越小,溶解氧浓度增量越大;洞塞长度越长,洞塞直径越小,溶解氧浓度增量越大。     

Humic substance charge determination by titration with a flexible cationic polyelectrolyte

The anionic charge of humic substances (HS) plays a major role in the interaction of HS with other components. Therefore, the potential of the polyelectrolyte titration technique to obtain the charge density of HS in simple 1-1 electrolyte solutions has been investigated. Titrations are carried out with an automatic titrator combined with the “Mütek particle charge detector” which allows determination of the Mütek potential and the pH as a function of the added amount of titrant which is a solution of poly-diallyldimethylammonium chloride (polyDADMAC), a cationic strong polyelectrolyte. When the Mütek potential reverses its sign the iso-electric point (IEP) of the polyDADMAC-HS complex is reached. The polyDADMAC/HS mass ratio at the IEP gives information on the HS charge density and from the pH changes in solution an estimate of the charge regulation in the HS-polyDADMAC complex can be obtained. In general, for polyDADMAC-HS complexes an increase in the dissociation of the acid groups of HS is found (charge regulation). The charge regulation decreases with increasing concentration of 1-1 background electrolyte. Cation incorporation can be neglected at 1-1 electrolyte concentrations ? 1 mmol L⁻¹ and a 1-1 stoichiometry exists between the polyDADMAC and HS charge. However, at these low salt concentrations the charge regulation is substantial. A detailed analysis of purified Aldrich humic acid (PAHA) at pH 5 and a range of KCl concentrations reveals that the anionic charge of PAHA in the complex increases at 5 mmol L⁻¹ KCl by 30% and at 150 mmol L⁻¹ KCl by 12%. On the other hand, increasing amounts of K⁺ become incorporated in the complex: at 5 mmol L⁻¹ KCl 5% and at 150 mmol L⁻¹ KCl 24% of the PAHA charge is balanced by K⁺. By comparing at pH 5 the mass ratios polyDADMAC/PAHA in the complex at the IEP with the theoretical mass ratios of polyDADMAC/PAHA required to neutralize PAHA in the absence of charge regulation and K⁺ incorporation, it is found that at 50 mmol L⁻¹ KCl the extra negative charge due to the interaction between polyDADMAC and PAHA is just compensated by K⁺ incorporation in the complex. Therefore, a pseudo 1-1 stoichiometry exists at about 50 mmol L⁻¹ 1-1 electrolyte concentration and only at this salt concentration polyDADMAC titrations and conventional proton titrations give identical results. Most likely this is also true for other HA samples and other pH values. For FA further study is required to reveal the conditions for which polyDADMAC and proton titrations give identical results.     

Adsorption of hydroxamate siderophores and EDTA on goethite in the presence of the surfactant sodium dodecyl sulfate

Siderophore-promoted iron acquisition by microorganisms usually occurs in the presence of other organic molecules, including biosurfactants. We have investigated the influence of the anionic surfactant sodium dodecyl sulfate (SDS) on the adsorption of the siderophores DFOB (cationic) and DFOD (neutral) and the ligand EDTA (anionic) onto goethite (α-FeOOH) at pH 6. We also studied the adsorption of the corresponding 1:1 Fe(III)-ligand complexes, which are products of the dissolution process. Adsorption of the two free siderophores increased in a similar fashion with increasing SDS concentration, despite their difference in molecule charge. In contrast, SDS had little effect on the adsorption of EDTA. Adsorption of the Fe-DFOB and Fe-DFOD complexes also increased with increasing SDS concentrations, while adsorption of Fe-EDTA decreased. Our results suggest that hydrophobic interactions between adsorbed surfactants and siderophores are more important than electrostatic interactions. However, for strongly hydrophilic molecules, such as EDTA and its iron complex, the influence of SDS on their adsorption seems to depend on their tendency to form inner-sphere or outer-sphere surface complexes. Our results demonstrate that surfactants have a strong influence on the adsorption of siderophores to Fe oxides, which has important implications for siderophore-promoted dissolution of iron oxides and biological iron acquisition.     

Enhanced removal of dissolved metal ions in radioactive effluents by flocculation

Decontamination of radioactive effluents of low or intermediate level of radioactivity generated from different nuclear industries is done through the chemical precipitation route. The precipitates thus formed are of very fine sizes thereby requiring flocculation for faster settlement. The presence of polyacrylamide-based polymer not only enhances settling velocity but also increases removal of dissolved non-radioactive as well as radioactive metal ions from the liquid. About 99.5% of Cu²⁺ and Fe³⁺ ions are removed due to the presence of cationic Rishabh 611. Flocculation by either cationic or anionic flocculant has shown improvement in removal of radioactive strontium while turbidity of the liquid is reduced to a very low value (0.8 NTU). Decontamination factors (DF) of the effluents from different plants are improved by 3–5 times.     

The effects of pH, ionic strength, and iron-fulvic acid interactions on the kinetics of non-photochemical iron transformations. I. Iron(II) oxidation and iron(III) colloid formation

Flow injection analysis was used to study the effect of a fulvic acid on the kinetics of iron(II) oxidation and iron colloid formation under conditions approximating fresh natural waters. While iron(II) oxidation in high-carbonate inorganic solutions is predicted well by a recently proposed homogeneous model, it overestimates the oxidation rate in low-carbonate solutions, possibly due to the formation of an intermediate iron(II) colloid or surface species. Results in fulvic acid solutions are consistent with the formation of an iron(II)-fulvic acid complex at both pH 6.0 and 8.0 which accelerates the overall oxidation rate relative to inorganic solutions. However, iron(III) complexation by fulvic acid greatly slows the formation of iron colloids, stabilizing dissolved iron(III). Decreased pH and increased ionic strength slow and decrease iron colloid formation. Evidence of a kinetic control on the distribution of iron(III) between organically complexed and colloidal forms is presented.