The effect of microorganisms on Fe precipitation rates at neutral pH

The effect of microorganisms on Fe precipitation rates at neutral pH in the field was examined. The studied area was a cave having Fe-stalactites composed mainly of ferrihydrite and associated microorganisms. The microorganisms were covered with ferrihydrite. Water associated with stalactites was slightly supersaturated with respect to ferrihydrite, and had a dissolved oxygen concentration of 2 ppm, a pH of 6, and an Fe concentration of approximately 14 ppm. Fe precipitation rates were estimated from decreases in Fe concentrations in water during flowing through the Fe-stalactites. The estimated Fe precipitation rate in the field ranges from 6.8×10⁻⁸ to 4.0×10⁻⁷ mol/l/s. These values are in good agreement with bulk estimates of Fe-stalactite growth rates derived from the length increase (1.3 cm) of one formation over 30 days. The estimated Fe precipitation rates are faster by about four orders of magnitude than expected inorganic precipitation rates. On-site Fe precipitation experiments with sterilized and unsterilized Fe-stalactites and without Fe-stalactites indicate that microorganisms are the controlling factor accelerating Fe precipitation rates at neutral pH. These results suggest that microbially accelerated Fe precipitation rates are more likely related to exopolysaccharides and microbial surface properties than metabolic precipitation mechanisms.     

The adsorption of aqueous heavy metals on inorganic minerals

Two models have been used to explain the in-situ control of heavy metals: (1) solubility controls, where precipitation of a solid phase occurs under varying metal and ligand concentrations, and (2) surface chemical controls, where adsorption or exchange occurs at the solid/solution interface. Based on experiments presented in this paper, surface chemical controls can account for the removal of heavy metals, particularly Zn(II), from metal solutions which are undersaturated with respect to the hydroxide, oxide, or other controlling solid phases. Adsorption isotherms are presented for varying solution pHs, total metal ion concentrations, ionic strengths, and mineral substrates. The minerals chosen for illustration are SiO₂, TiO₂, FeOOH, Al₂O₃, MnO_x and HgS which range widely in surface acidity, electrical double layer properties, specific surface areas, and surface functional groups.     

The effect of crystal orientation on the wetting behaviour of silicate melts on the surfaces of spinel peridotite minerals

. The effect of crystal anisotropy on wetting angles of equilibrium silicate melts on crystal faces of spinel, diopside, enstatite and olivine has been determined experimentally by the sessile melt drop technique. The anisotropy, Ãg_SL{\rm \~A}\gamma _{{\rm SL}} , of solid-liquid interfacial energies (%_SL(max)-%_SL(min)) can be related to the wetting angles, N, by Ãg_SL μ | cosy(max)  - cosy(min) | = Pw_{( [(A)\tilde]gSL )}{\rm \~A}\gamma _{{\rm SL}} \propto \left| {\cos \psi (\max )\; - \cos \psi (\min )} \right| = Pw_{\left( {{\rm \tilde A}\gamma _{{\rm SL}} } \right)} . Normalising to the smallest wetting angle gives values of Pw for diopside=0.0728, olivine=0.0574, orthopyroxene=0.0152, and spinel=0.0075. Crystal anisotropy influences grain-scale morphology of small-degree partial melts, permeability and the melt connectivity threshold, J_C. Results show that, at sufficient melt fractions, diopside should increase permeability in a peridotitic matrix, whereas enstatite should lower it. Despite its low anisotropy, spinel contributes positively to permeability and J_C because of its high surface energies. These results suggest that harzburgitic mineral matrices typical of the subcratonic mantle should impede the movement of low-degree partial melts, whereas melts should flow more easily through spinel lherzolites.     

The petrogenesis of L-6 chondrites: insights from the chemistry of minerals

Major, minor and trace element concentrations have been measured in all the volumetrically significant minerals from the L-6 chondrites Alfianello, Colby (WI) and Leedey. Most of the elements show the compositional uniformity observed in other studies. However, REE, Co and Ni are distinctly different in their abundances and their phase distributions in each of the three meteorites. Such differences must manifest differing physical and chemical conditions involved in the formation of each of the three rocks. The distributions of REE and Ni between various phases are compatible with models which assume equilibrium between presently coexisting minerals. Such a model demonstrates how plausible differences in temperature and Ni content of metallic minerals could produce the observed differences in Ni abundances in olivine and clinopyroxene from each of the three chondrites.REE are too abundant in the minerals to have been produced by crystal-liquid fractionation from a magma of whole rock composition.Alkali element abundances are incompatible with a model of closed system equilibration of the meteorites. Rb is underabundant in feldspar relative to Na when compared to the equilibrium model predictions. A portion of the Cs seems to be included in feldspar by diadochic substitution, however, significant amounts are randomly associated with other minerals, perhaps by incorporation into lattice defects and at interstices. Partial loss of this nonfeldspathic Cs may be responsible for the large range of Cs abundances observed in chondrites.     

The effect of silica and natural organic matter on the Fe(II)-catalysed transformation and reactivity of Fe(III) minerals

The Fe(II)-catalysed transformation of synthetic schwertmannite, ferrihydrite, jarosite and lepidocrocite to more stable, crystalline Fe(III) oxyhydroxides is prevented by high, natural concentrations of Si and natural organic matter (NOM). Adsorption isotherms demonstrate that Si adsorbs to the iron minerals investigated and that increasing amounts of adsorbed Si results in a decrease in isotope exchange between aqueous Fe(II) and the Fe(III) mineral. This suggests that the adsorption of Si inhibits the direct adsorption of Fe(II) onto the mineral surface, providing an explanation for the inhibitory effect of Si on the Fe(II)-catalysed transformation of Fe(III) minerals. During the synthesis of lepidocrocite and ferrihydrite, the presence of equimolar concentrations of Si and Fe resulted in the formation of 2-line ferrihydrite containing co-precipitated Si in both cases. Isotope exchange experiments conducted with this freeze-dried Si co-precipitated ferrihydrite species (Si-ferrihydrite) demonstrated that the rate and extent of isotope exchange between aqueous Fe(II) and solid ⁵⁵Fe(III) was very similar to that of 2-line ferrihydrite formed in the absence of Si and which had not been allowed to dry. In contrast to un-dried ferrihydrite formed in the absence of Si, Si-ferrihydrite did not transform into a more crystalline Fe(III) mineral phase over the 7-day period of investigation. Reductive dissolution studies using ascorbic acid demonstrated that both dried Si-ferrihydrite and un-dried 2-line ferrihydrite were very reactive, suggesting these species may be major contributors to the rapid release of dissolved iron following flooding and the onset of conditions conducive to reductive dissolution in acid sulphate soil environments.     

The effect of early diagenesis on the Fe isotope compositions of porewaters and authigenic minerals in continental margin sediments

Iron isotope compositions in marine pore fluids and sedimentary solid phases were measured at two sites along the California continental margin, where isotope compositions range from δ⁵⁶Fe = −3.0‰ to +0.4‰. At one site near Monterey Canyon off central California, organic matter oxidation likely proceeds through a number of diagenetic pathways that include significant dissimilatory iron reduction (DIR) and bacterial sulfate reduction, whereas at our other site in the Santa Barbara basin DIR appears to be comparatively small, and production of sulfides (FeS and pyrite) was extensive. The largest range in Fe isotope compositions is observed for Fe(II)_aq in porewaters, which generally have the lowest δ⁵⁶Fe values (minimum: −3.0‰) near the sediment surface, and increase with burial depth. δ⁵⁶Fe values for FeS inferred from HCl extractions vary between ∼−0.4‰ and +0.4‰, but pyrite is similar at both stations, where an average δ⁵⁶Fe value of −0.8 ± 0.2‰ was measured. We interpret variations in dissolved Fe isotope compositions to be best explained by open-system behavior that involves extensive recycling of Feflux. This study is the first to examine Fe isotope variations in modern marine sediments, and the results show that Fe isotopes in the various reactive Fe pools undergo isotopic fractionation during early diagenesis. Importantly, processes dominated by sulfide formation produce high-δ⁵⁶Fe values for porewaters, whereas the opposite occurs when Fe(III)-oxides are present and DIR is a major pathway of organic carbon respiration. Because shelf pore fluids may carry a negative δ⁵⁶Fe signature it is possible that the Fe isotope composition of ocean water reflects a significant contribution of shelf-derived iron to the open ocean. Such a signature would be an important means for tracing iron sources to the ocean and water mass circulation.     

The effects of organic acids on the dissolution of silicate minerals: A case study of oxalate catalysis of kaolinite dissolution

Most studies agree that the dissolution rate of aluminosilicates in the presence of oxalic and other simple carboxylic acids is faster than the rate with non-organic acid under the same pH. However, the mechanisms by which organic ligands enhance the dissolution of minerals are in debate. The main goal of this paper was to study the mechanism that controls the dissolution rate of kaolinite in the presence of oxalate under far from equilibrium conditions (−29 < ΔG_r < −18 kcal mol⁻¹). Two types of experiments were performed: non-stirred flow-through dissolution experiments and batch type adsorption isotherms. All the experiments were conducted at pH 2.5-3.5 in a thermostatic water-bath held at a constant temperature of 25.0, 50.0 or 70.0 ± 0.1 °C. Kaolinite dissolution rates were obtained based on the release of silicon and aluminum at steady state. The results show good agreement between these two estimates of kaolinite dissolution rate. At constant temperature, there is a general trend of increase in the overall dissolution rate as a function of the total concentration of oxalate in solution. The overall kaolinite dissolution rates in the presence of oxalate was up to 30 times faster than the dissolution rate of kaolinite at the same temperature and pH without oxalate as was observed in our previous study. Therefore, these rate differences are related to differences in oxalate and aluminum concentrations. Within the experimental variability, the oxalate adsorption at 25, 50, and 70 °C showed the same dependence on the sum of the activities of oxalate and bioxalate in solution. The change of oxalate concentration on the kaolinite surface (C_s,ox) as a function of the sum of the activities of the oxalate and bioxalate in solution may be described by the general adsorption isotherm:

     

The effect of Al3+, Fe3+, and Ti4+ on the configurational heat capacities of sodium silicate liquids

The heat capacities of 29 glasses and supercooled liquids in the Na₂O-SiO₂, Na₂O-Al₂O₃-SiO₂, Na₂O-(FeO)-Fe₂O₃-SiO₂, and Na₂O-TiO₂-SiO₂ systems were measured in air from 328 to 998 K with a differential scanning calorimeter. The reproducibility of the data determined from multiple heat capacity runs on a single crystal MgO standard is within ± 1% of the accepted values at temperatures ≤ 800 K and within ± 1.5% between 800 and 1000 K. Within the resolution of the data, the heat capacities of sodium silicate and sodium aluminosilicate liquids are temperature independent. Heat capacity data in the supercooled liquid region for the sodium silicates and sodium aluminosilicates were combined and modelled assuming a linear compositional dependence. The derived values for the partial molar heat capacities of Na₂O, Al₂O₃, and SiO₂ are 112.35 ± 0.42, 153.16 ± 0.82, and 76.38 ± 0.20 J/gfw · K respectively. The partial molar heat capacities of Fe₂O₃ and TiO₂ could not be determined in the same manner because the heat capacities of the Fe₂O₃- and TiO₂-bearing sodium silicate melts showed varying degrees of negative temperature dependence. The negative temperature dependence to the configurational C _P may be related to the occurrence of sub-microscopic domains (relatively polymerized and depolymerized) that break down to a more homogeneous melt structure with increasing temperature. Such an interpretation is consistent with data from in situ Raman, Mössbauer, and X-ray absorption fine structure (XAFS) spectroscopic studies on similar melts.     

The effect of extracellular polymers (EPS) on the proton adsorption characteristics of the thermophile Bacillus licheniformis S-86

This study investigated proton adsorption to an extracellular polymeric substance (EPS) producing bacterial strain, Bacillus licheniformis S-86, in order to characterise and quantify the contribution made by EPS to cell surface reactivity. Potentiometric titrations were conducted using both untreated cells and cells from which the EPS layer had been extracted. Surface-complexation modelling indicated the presence of four different functional groups in both untreated and EPS-free cells. These sites are assigned to phosphodiester, (pK_a 3.3–3.4), carboxylic (pK_a 5.3–5.4), phosphoryl/ (pK_a 7.4–7.5) and hydroxyl/amine (pK_a 9.9–10.1) type groups. The pK_a values for the four groups were very similar for untreated and EPS-free cells, indicating no qualitative difference in composition, but site concentrations in the untreated cells were statistically found to be significantly higher than those in the EPS-free cells for the pK_a 3.3–3.4 and pK_a 9.9–10.1 sites. Infrared analysis provided supporting evidence that site 2 is carboxylic in nature but did not reveal any difference in IR absorption between the native and EPS-free cells. Dissolved organic carbon (DOC) analysis conducted during this study indicated that DOC release by cells is significant, and that the EPS layer is the major contributor.     

The effect of net-transfer reactions on the isotopic composition of minerals

To interpret correctly the isotopic composition of metmorphic rocks and minerals, the effect of nettransfer reactions must be quantitatively evaluated. Such evaluation requires a complete set of linearly independent, net-transfer reactions that fully describe the reacting system. The set of net-transfer reactions is then coupled with mass-balance equations for stable isotopes. Reaction spaces can be contoured with isopleths of °¹⁸O, °¹³C, and D of minerals which allows evaluation of the effect of different reactions and bulk compositions on the stable isotopic composition of minerals and rocks. Using this approach, we examined the effect of fractionation of isotopes due to net-transfer reactions at the biotite and second-sillimanite isograds in northern New England. Our analysis shows that the shift in °¹³C and °¹⁸O at an isograd depends strongly upon the overall net-transfer reaction at the isograd and the bulk composition of the rock. The use of model isograd reactions to determine isotopic shifts, therefore, can lead to serious errors in the interpretation of isotopic data. At the second-sillimanite isograd °¹⁸O _qtz (quartz), °¹⁸O _kspar (K feldsdpar), and °¹⁸O _wr (whole rock) decrease by 0.5, 1.0, and 0.8 per mil, respectively. Quantitative evaluation of the effect of fractionation of isotopes by net-transfer reactions shows that: (1) the relative changes in oxygen isotopes across the isograd could be caused by distillation of fluids during develatilization reactions; (2) the magnitude of the observed isotopic shifts often differs by a factor of 2 from the calculated shifts due to reaction progress alone. The difference between observed and calculated shifts is attributed to either, differences in bulk composition between individual rocks, or, to isotopic exchange between minerals after peak metamorphism. At the biotite isograd the shifts in carbon and oxygen isotope values are different from predicted shifts caused by net-transfer reactions alone. This discrepancy suggests that fluids infiltrated the rocks during the formation of the biotite isograd.     

Formation of solid bituminous matter in pegmatites: Constraints from experimentally formed organic matter on microporous silicate minerals

The formation of solid bituminous matter (SBM) on surfaces of microporous silicates was experimentally studied at pressure and temperature conditions typical of late-stage magmatic and hydrothermal processes. Aliquots of microporous silicate minerals (zorite and kuzmenkoite-Mn, Lovozero Alkaline Massif, Kola Peninsula, Russia) were exposed to solid or liquid organic carbon sources (natural brown coal and liquid 1-hexene for synthesis purposes) in a 0.1 M NaCl-solution for 7 days, at constant pressure (50 MPa), and at three individual temperatures (200, 275, and 300 °C). No thermal decomposition of the solid organic sources happened at 200 °C and only a thin film of brown coal derivatives on the silicates’ surfaces and no formation of SBM were observed at 275 °C and 300 °C. But solid bituminous matter on the surfaces of both microporous silicates were detected in experiments with liquid 1-hexene as organic carbon source and at temperatures of 275 °C and 300 °C with a more pronounced formation of SBM at 300 °C compared to 275 °C. The aromatic and aliphatic hydrocarbons, as well as alcoholic compounds of the experimentally produced SBM are similar, if not even partly identical, with natural SBM occurrences of the Khibiny and Lovozero Massifs, Kola Peninsula, Russia, and from the Viitaniemi granitic pegmatite, Finland, as shown by FT-IR and ¹H NMR spectroscopy. This strengthens the hypothesis of formation of natural solid bituminous matter by catalytic reactions between microporous Ti-, Nb- and Zr-silicates and hydrocarbons at postmagmatic hydrothermal conditions.     

Influence of sodium silicate addition on the adsorption of oleic acid by fluorite,calcite and barite

A study has been made of the adsorption of sodium silicate by calcite, fluorite and barite and the effect that this adsorption has on the flotation of these minerals with oleic acid. The results show that sodium silicate depresses these minerals by preventing oleate species from reacting with surface sites. This effect is independent of the total silica concentration. Aged sodium silicate solutions do not produce markedly different results to those obtained with fresh solutions.The concentration of the sodium silicate solutions was generally such that the total silica concentration was below that in equilibrium with amorphous silica. Under these conditions the solutions contained no polymeric silica species and the mechanism of silica adsorption can be generally attributed to interactions of monosilicate ion and monosilicic acid with surface sites.     

The effect of garnet cell volume on the distribution of Mg and Fe in garnet exchange equilibria

The distribution of Mg in garnet exchange equilibria has been examined in three regional metamorphic and four eclogitic parageneses. Garnet cell volume has been found to have a significant effect on the distribution of Mg between garnet and coexisting ferromagnesian minerals. When the activity of Mg is corrected for the variation in cell volume, the range in variation of the distribution coefficients is strongly reduced within each group. Also the relative positions of the different groups in the distribution diagrams are in better accordance with geological evidence of crystallization temperatures. It is proposed that the effect of the garnet cell volume on the Mg distribution may be used as a geobarometer. The distribution of Ca between garnet and plagioclase is also discussed and it is found that the Ca partitioning is not suitable for geobarometry, as this partioning is dependent on the Mg/Fe ratio of the garnet.     

The effect of pressure on the solubility of minerals in water and seawater

The effect of presure on the solubility of minerals in water and seawater can be estimated from In

$\text{(}\text{K}{}^{\mathrm{P}}{}_{\mathrm{sp}}\text{K}{}^0{}_{\mathrm{sp}}\text{) +}\text{(?ΔVP + 0.5ΔKP}{}^2\text{)}\text{RT}$

where the volume (ΔV) and compressibility (ΔK) changes at atmospheric pressure (P = 0) are given by

$\text{ΔV =}\text{V}\text{?}\text{(M}{}^{\mathrm{+}}\text{, X}{}^{\mathrm{?}}\text{) ?}\text{V}\text{?}\text{[MX(s)]ΔK =}\text{K}\text{?}\text{(M}{}^{\mathrm{+}}\text{, X}{}^{\mathrm{?}}\text{) ?}\text{K}\text{?}\text{[MX(s)]}$

Values of the partial molal volume ($\text{V}\text{?}$) and compressibilty ($\text{K}\text{?}$) in water and seawater have been tabulated for some ions from 0 to 50°C. The compressibility change is quite large (~10 × 10^?3 cm³ bar^?1 mol^?1) for the solubility of most minerals. This large compressibility change accounts for the large differences observed between values of ΔV obtained from linear plots of In K_sp versus P and molal volume data (Macdonald and North, 1974; North, 1974). Calculated values of $\text{K}{}^{\mathrm{P}}{}_{\mathrm{sp}}\text{K}{}^{\mathrm{o}}{}_{\mathrm{sp}}$ for the solubility of CaCO₃, SrSO₄ and CaF₂ in water were found to be in good agreement with direct measurements (Macdonald and North, 1974). Similar calculations for the solubility of minerals in seawater are also in good agreement with direct measurements (Ingle, 1975) providing that the surface of the solid phase is not appreciably altered.     

The compressibility of silicate liquids containing Fe2O3 and the effect of composition,temperature, oxygen fugacity and pressure on their redox states

Ultrasonic longitudinal acoustic velocities in oxidized silicate liquids indicate that the pressure derivative of the partial-molar volume of Fe₂O₃ is the same in iron-rich alkali-, alkaline earth- and natural silicate melt compositions at 1 bar. The dV/dP for multicomponent silicate liquids can be expressed as a linear combination of partial-molar constants plus a positive excess term for Na₂O−Al₂O₃ mixing. Partial-molar properties for FeO and Fe₂O₃ components allow extension of the empirical expression of Sack et al. (1980) to permit the calculation of Fe-redox equilibrium in a natural silicate liquid as a function of composition, temperature, fo₂ and pressure; a more formal thermodynamic expression is presented in the Appendix. The predicted equilibrium fo₂ of natural silicate melts, of fixed oxygen content, closely parallels that defined by the metastable assemblage fayalite+magnetite+β-quartz (FMQ), in pressure-temperature space. A silicate melt initially equilibrated at 3 GPa and FMQ, will remain within approximately 0.5 log₁₀ units of FMQ during its closed-system ascent. Thus, for magmas closed to oxygen, iron-redox equilibrium in crystal-poor pristine glassy lavas represents an excellent probe of the relative oxidation state of their source regions.     

Mineralogical and morphological constraints on the reduction of Fe(III) minerals by Geobacter sulfurreducens

The biologically-mediated reduction of synthetic samples of the Fe(III)-bearing minerals hematite, goethite, lepidocrocite, feroxhyte, ford ferrihydrite, akaganeite and schwertmannite by Geobacter sulfurreducens has been investigated using microbiological techniques in conjunction with X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). This combination of approaches offers unique insights into the influence of subtle variations in the crystallinity of a given mineral on biogeochemical processes, and has highlighted the importance of (oxyhydr)oxide crystallite morphology in determining the changes occurring in a given mineral phase. Problems arising from normalising the biological Fe(III) reduction rates relative to the specific surface areas of the starting materials are also highlighted. These problems are caused primarily by particle aggregation, and compounded when using spectrophotometric assays to monitor reduction. For example, the initial rates of Fe(III) reduction observed for two synthetic feroxyhytes with different crystallinities (as shown by XRD and TEM studies) but almost identical surface areas, differ substantially. Both microbiological and high-resolution TEM studies show that hematite and goethite are susceptible to limited amounts of Fe(III) reduction, as evidenced by the accumulation of Fe(II) during incubation with G. sulfurreducens and the growth of nodular structures on crystalline goethite laths during incubation. Lepidocrocite and akaganeite readily transform into mixtures of magnetite and goethite, and XRD data indicate that the proportion of magnetite increases within the transformation products as the crystallinity of the starting material decreases. The presence of anthraquinone-2,6-disulfonate (AQDS) as an electron shuttle increases both the initial rate and longer term extent of biological Fe(III) reduction for all of the synthetic minerals examined. High-resolution XPS indicates subtle but measurable differences in the Fe(III):Fe(II) ratios at the mineral surfaces following extended incubation. For example, for a poorly crystalline schwertmannite, deconvolution of the Fe2p_3/2 peak suggests that the Fe(III):Fe(II) ratio of the near-surface regions varies from 1.0 in the starting material to 0.9 following 144 h of incubation with G.sulfurreducens, and to 0.75 following the same incubation period in the presence of 10 μM AQDS. These results have important implications for the biogeochemical cycling of iron.     

The effect of melt composition on the wetting angle between silicate melts and olivine

The wetting angle between silicate melts containing Ca, Li, Na, or K and olivine single crystals have been measured as part of an investigation of the dependence of the solid-liquid interfacial energy on melt composition and olivine orientation. The wetting angle increases with increasing silica content of the melt on (100) surfaces, but decreases with increasing silica content on (010) and (001) surfaces. For a given silica content, the wetting angle on (100) decreases in going from Ca to Li to Na to K, while the wetting angle on (010) and (001) increases in going from Ca to K-bearing melts. Based on published values for liquid-vapor interfacial energies, the observed changes in wetting angle with changes in melt composition indicate that the solid-liquid interfacial energy increases with increasing silica content of the melt for the (100) surface. However, for (010) and (001) surfaces, the variation of the solid-liquid interfacial energy with silica content depends upon whether Ca or K is present in the melt. In addition, the solid-liquid interfacial energy depends upon the orientation of the olivine in the following manner: _sl ⁽⁰¹⁰⁾ _sl ⁽⁰⁰¹⁾ _sl ⁽¹⁰⁰⁾ .     

The effect of titanium and phosphorus on ferric/ferrous ratio in silicate melts: an experimental study

The effect of TiO₂ and P₂O₅ on the ferric/ferrous ratio in silicate melts was investigated in model silicate melts at air conditions in the temperature range 1,400–1,550 °C at 1-atm total pressure. The base composition of the anorthite–diopside eutectic composition was modified with 10 wt % Fe₂O₃ and variable amounts of TiO₂ (up to 30 wt %) or P₂O₅ (up to 20 wt %). Some compositions also contained higher SiO₂ concentrations to compare the role of SiO₂, TiO₂, and P₂O₅ on the Fe³⁺/Fe²⁺ ratio. The ferric/ferrous ratio in experimental glasses was analyzed using a wet chemical technique with colorimetric detection of ferrous iron. It is shown that at constant temperature, an increase in SiO₂, TiO₂, and P₂O₅ content results in a decrease in the ferric/ferrous ratio. The effects of TiO₂ and SiO₂ on the Fe³⁺/Fe²⁺ ratio was found to be almost identical. In contrast, adding P₂O₅ was found to decrease ferric/ferrous ratio much more effectively than adding silica. The results were compared with the predictions from the published empirical equations forecasting Fe³⁺/Fe²⁺ ratio. It was demonstrated that the effects of TiO₂ are minor but that the effects of P₂O₅ should be included in models to better describe ferric/ferrous ratio in phosphorus-bearing silicate melts. Based on our observations, the determination of the prevailing fO₂ in magmas from the Fe³⁺/Fe²⁺ ratio in natural glasses using empirical equations published so far is discussed critically.