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Redox potential sorption

In addition to effects on the concentration of anions, the redox potential can affect the oxidation state and solubility of the metal ion directly. The most important examples of this are the dissolution of iron and manganese under reducing conditions. The oxidized forms of these elements (Fe(III) and Mn(IV)) form very insoluble oxides and hydroxides, while the reduced forms (Fe(II) and Mn(II)) are orders of magnitude more soluble (in the absence of S( — II)). The oxidation or reduction of the metals, which can occur fairly rapidly at oxic-anoxic interfaces, has an important "domino" effect on the distribution of many other metals in the system due to the importance of iron and manganese oxides in adsorption reactions. In an interesting example of this, it has been suggested that arsenate accumulates in the upper, oxidized layers of some sediments by diffusion of As(III), Fe(II), and Mn(II) from the deeper, reduced zones. In the aerobic zone, the cations are oxidized by oxygen, and precipitate. The solids can then oxidize, as As(III) to As(V), which is subsequently immobilized by sorption onto other Fe or Mn oxyhydroxide particles (Takamatsu et al, 1985). [Pg.390]

Sorption of pharmaceuticals onto the surface of particulate matter or their distribution between two phases (water and either sludge, sediment or soil) depends on many factors, the most important being liquid phase pH and redox potential, the stereochemical structure and chemical nature of both the pharmaceutical compound and the sorbent, the lipophilicity of the sorbed molecules (excellent sorption at log Kov > 4, low sorption at log < 2.4), the sludge-water distribution coefficient Kd Kd > 2 L g SS good sorption, < 0.3 L g SS low sorption), the extent of neutral and ioiuc species present in the wastewater and the characteristics of the suspended particles. Moreover, the presence of humic and fulvic substances may alter the surface properties of the sludge, as well as the number of sites available for sorption and reactions, thereby enhancing or suppressing sorption of PhCs [38, 55, 61]. [Pg.150]

CuS and Ag2S were the only synthesized metal sulfides to removed Hg(0) vapors from air. The commercial grade Ag2S, AU2S, and AU2S3 also removed Hg(0). The redox potentials of the constituent metals are listed in Table 1 [9]. Although the standard potentials listed are for metals in acidic solutions, the values correlate with the observed Hg(0)-sorption results, that is, only those metal sulfide powders containing metals with positive reduction potential were effective. [Pg.769]

The groundwater transport of radionuclides through waterbearing interbed layers in the Columbia River basalt formation will be controlled by reactions of the radionuclides with groundwater and interbed solids. These interactions must be understood to predict possible migration of radionuclides from a proposed radioactive waste repository in basalt. Precipitation and sorption on interbed solids are the principle reactions that retard radionuclide movement in the interbeds. The objective of the work described herein was to determine the sorption and desorption behavior of radionuclides important to safety assessment of a high-level radioactive waste repository in Columbia River basalt. The effects of groundwater composition, redox potential, radionuclide concentration, and temperature on these reactions were determined. [Pg.9]

Effects of Groundwater Composition and Eh. Radionuclide sorption on geologic solids is dependent on the chemical composition of the groundwater solution and the redox potential (Eh) of the solid-groundwater system. Aquifers at various depths in the Columbia Plateau formation have -been observed to have significant differences in composition. To accurately model radionuclide migration, it is necessary to understand the effects of chemical components and Eh on sorption and solubility of key radionuclides. An additional benefit of this work is to better understand the mechanisms of sorption and desorption of the radionuclides. [Pg.21]

In most natural water, phosphine is very unstable and oxidizes even under anoxic conditions. Depending upon the redox potential of water, the oxidation products are diphosphine (P2H4), phosphorus, hypophosphorus acid, phosphorus acid, and phosphoric acid (Kumar et al. 1985). Based on soil studies (Berck and Gunther 1970 Hilton and Robison 1972), small amounts of phosphine may also be adsorbed (reversible sorption) or chemisorbed (irreversible sorption) to suspended solid and sediments in water. However, based on the estimated Henry s law constant (H) of 0.09 atm-m3/mol (see Table 3-3) and the expected volatility associated with various ranges of H, volatilization is expected to be the most important loss process for phosphine in water. [Pg.192]

Many adsorbates and/or adsorbents are redox sensitive. The specific adsorption in such systems depends on the redox potential, which is very difficult to measure or control, thus, systematic studies in this direction are rare. On the other hand some practical implications are well known, e.g. the uptake of chromates by soils and sediments in enhanced on addition of Fe(II) salts [27] as an effect of a redox reaction, in which Cr(VI) is reduced to Cr(III). A few examples of redox reactions accompanying sorption processes are reported in the column results". The changes of oxidation state in the sorption process are probably more common than it is apparent from literature reports, but they are often overlooked, namely, analytical methods must be specially tailored to observe these changes. [Pg.326]

Quantity/intensity relationships are often used to describe soil capacity to buffer phosphorus concentration in soil pore water. The quantity (0 refers to the amount of phosphorus adsorbed on soil surface, whereas intensity (/) refers to the concentration of P in soil pore water. This ratio can also be viewed as partition coefficient (K ), as indicated by liner sorption isotherms. The ratio expressed as either QII or is influenced by various physicochemical properties of soils, including clay content, high concentration of Fe and Al oxides, CaCOj content, organic matter content, pH, and redox potential. [Pg.350]

Dissolved oxygen can oxidize Cr(III) to Cr(VI) however, the oxidation is slow at normal temperature in aqueous environments. Due to the slow oxidation, Cr(lll) is involved in faster sorption and precipitation reactions. Similar results were obtained by Masscheleyn et al. (1992) investigating Cr(III) oxidation as affected by the soil redox potential. In this reported soil study, Cr(III) was... [Pg.497]

The results indicate that Fe oxides and potential redox are the main soil properties controlling arsenic sorption rate. Yellow Latosol adsorbed less arsenic presumably because of its kaolinite content. Kaolin particles which had clean surfaces and low ferric oxide contents showed no uptake of As (V). The soluble arsenate was controlled by adsorption/co-precipitation in soils. Both parameters (redox potential and Fe presence) are important in assessing the fate of arsenic-containing compounds in soil therefore, at higher redox levels arsenate were the predominant As species and their sol-ubihty was low. Due to the slow kinetics of the As (V) - As (III) transformation, a considerable amount of the thermodynamically unstable arsenate species was observed under reducing conditions. [Pg.239]

Using these examples, and the case study from the Aspo Hard Rock Laboratory, we summarize two linked principles for the redox-related performance of sub-surface repositories and the risk posed by wastes in the geosphere. Redox potentials need to be considered as critical thresholds for many controlling processes corrosion of engineered barriers, solubility and sorption of metals and attenuation of organic contaminants through biodegradation. Redox capacities, on the other hand, indicate the total amount of reductants or oxidants required to maintain redox conditions above or below these critical thresholds for performance and risk. [Pg.98]

Investigations of redox processes in natural water systems have emphasized the disequilibrium behavior of many couples (e.g., 37). The degree of coupling of redox reactions with widely varying rates, and its effect on radionuclide transport in an NWRB needs to be considered. Because of the generally slow kinetics of autoxidation reactions, the potential surface catalyzed reduction of a radionuclide at low temperatures in the presence of trace levels of DO may explain certain sorption data (e.g., 38). [Pg.189]

Oxidation-reduction (redox) reactions, along with hydrolysis and acid-base reactions, account for the vast majority of chemical reactions that occur in aquatic environmental systems. Factors that affect redox kinetics include environmental redox conditions, ionic strength, pH-value, temperature, speciation, and sorption (Tratnyek and Macalady, 2000). Sediment and particulate matter in water bodies may influence greatly the efficacy of abiotic transformations by altering the truly dissolved (i.e., non-sorbed) fraction of the compounds — the only fraction available for reactions (Weber and Wolfe, 1987). Among the possible abiotic transformation pathways, hydrolysis has received the most attention, though only some compound classes are potentially hydrolyzable (e.g., alkyl halides, amides, amines, carbamates, esters, epoxides, and nitriles [Harris, 1990 Peijnenburg, 1991]). Current efforts to incorporate reaction kinetics and pathways for reductive transformations into environmental exposure models are due to the fact that many of them result in reaction products that may be of more concern than the parent compounds (Tratnyek et al., 2003). [Pg.324]

Experimental studies. Sorption of radionuclides by colloids is affected by the same solution composition parameters discussed in the previous section on sorption processes. The important parameters include pH, redox conditions, the concentrations of competing cations such as Mg " " and K, and the concentrations of organic ligands and carbonate. The high surface area of colloids leads to relatively high uptake of radionuclides compared to the rock matrix. This means that a substantial fraction of mobile radionuclides could be associated with carrier colloids in some systems. The association of radionuclides with naturally occurring colloids and studies of radionuclide uptake by colloids in laboratory systems give some indication of the potential importance of colloid-facilitated radionuclide transport in the environment as discussed below. [Pg.4779]

The formation of 2D Meads phases on a foreign substrate, S, in the underpotential range can be well described considering the substrate-electrolyte interface as an ideally polarizable electrode as shown in Section 8.2. In this case, only sorption processes of electrolyte constituents, but no Faradaic redox reactions or Me-S alloy formation processes are allowed to occur, The electrochemical double layer at the interface can be thermodynamically considered as a separate interphase [3.54, 3.212, 3.213]. This interphase comprises regions of the substrate and of the electrolyte with gradients of intensive system parameters such as chemical potentials of ions and electrons, electric potentials, etc., and contains all adsorbates and all surface energy. Furthermore, it is assumed that the chemical potential //Meads is a definite function of the Meads surface concentration, F, and the electrode potential, E, at constant temperature and pressure Meads (7", ). Such a model system can only be... [Pg.43]


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