Formation of hydroxyl radicals catalyzed by clay surfaces

 The formation of superoxide and hydroxyl radicals at the surface of smectite clays due to oxygen reduction is demonstrated by electron paramagnetic resonance spectroscopy. The yield of hydroxyl radicals is mainly a function of particle size of the clays and depends, to a lesser extent, on the clay lattice iron. Synthetic laponite clay with small platelet size (∼20 nm) and without lattice iron is leading in the formation of hydroxyl radicals followed by montmorillonite (∼200 nm). Fluorohectorite (∼2000 nm) was inactive to hydroxyl radical formation by oxygen reduction. Received: 20 January 2001 / Accepted: 7 August 2001     

Role of hydrogen peroxide and hydroxyl radical in pyrite oxidation by molecular oxygen

Hydrogen peroxide and hydroxyl radical are readily formed during the oxidation of pyrite with molecular oxygen over a wide range of pH conditions. However, pretreatment of the pyrite surface influences how much of the intermediates are formed and their fate. Acid-washed pyrite produces significant amounts of hydrogen peroxide and hydroxyl radical when suspended in air-saturated water. However, the hydrogen peroxide concentration shows an exponential decrease with time. Suspensions made with partially oxidized pyrite yield significantly lower amounts of hydrogen peroxide product. The presence of Fe(III)-oxide or Fe(III)-hydroxide patches facilitates the conversion of hydrogen peroxide to oxygen and water. Hence, the degree to which a pyrite surface is covered with patches of Fe(III)-oxide or Fe(III)-hydroxide patches is an important control on the concentration of hydrogen peroxide in solution.Hydrogen peroxide appears to be an important intermediate in the four-electron transfer from pyrite to molecular oxygen. Addition of catalase, an enzyme that decomposes hydrogen peroxide to water and molecular oxygen, to a pyrite suspension reduces the oxidation rate by 40%. By contrast, hydroxyl radical does not appear to play a significant role in the oxidation mechanism. It is estimated on the basis of a molecular oxygen and sulfate mass balance that 5-6% of the molecular oxygen is consumed without forming sulfate.     

The hydroxyl content of staurolite

Contributions to Mineralogy and Petrology - The composition of forty-six staurolite samples spanning a range in metamorphic grade has been determined by electron microprobe analysis and an improved...     

Pressure dependence of hydroxyl solubility in coesite

 The solubility of hydroxyl in coesite was investigated in multianvil experiments performed at 1200 °C over the nominal pressure range 5–10 GPa, at an f _O2 close to the Ni-NiO buffer. The starting material for each experiment was a cylinder of pure silica glass plus talc, which dehydrates at high P and T to provide a source of water and hydrogen (plus enstatite and excess SiO₂). Fourier-transform infrared (FTIR) spectra of the recovered coesite crystals show five sharp bands at 3606, 3573, 3523, 3459, and 3299 cm⁻¹, indicative of structurally bonded hydrogen (hydroxyl). The concentration of hydrogen increases with pressure from 285 H/10⁶ Si (at 5 GPa) to 1415 H/10⁶ Si (at 10 GPa). Assuming a model of incorporation by (4H)_Si defects, the data are fit well by the equation C _OH=Af ² _H2<\INF>Oexp(−PΔV/RT), with A=4.38 H/10⁶ Si/GPa, and ΔV=20.6 × 10⁻⁶ m³ mol⁻¹. An alternative model entailing association of hydrogen with cation substitution can also be used to fit the data. These results show that the solubility of hydroxyl in coesite is approximately an order of magnitude lower than in olivines and pyroxenes, but comparable to that in pyropic garnet. However, FTIR investigations on a variety of ultrahigh pressure metamorphic rocks have failed in all cases to detect the presence of water or hydrogen in coesite, indicating either that it grew in dry environments or lost its hydrogen during partial transformation to quartz. On the other hand, micro-FTIR investigations of quartz crystals replacing coesite show that they contain varying amounts of H₂O. These results support the hypothesis that preservation of coesite is not necessarily linked to fast exhumation rates but is crucially dependent on limited fluid infiltration during exhumation. Received: 23 August 1999 / Accepted: 10 April 2000     

Aqueous pyrite oxidation by dissolved oxygen and by ferric iron

Rates of aqueous, abiotic pyrite oxidation were measured in oxygen-saturated and anaerobic Fe(III)-saturated solutions with initial pH from 2 to 9. These studies included analyses of sulfite, thiosulfate, polythionates and sulfate and procedures for cleaning oxidation products from pyrite surfaces were evaluated. Pyrite oxidation in oxygen-saturated solutions produced (1) rates that were only slightly dependent on initial pH, (2) linear increases in sulfoxy anions and (3) thiosulfate and polythionates at pH > 3.9. Intermediate sulfoxy anions were observed only at high stirring rates. In anaerobic Fe(III)-saturated solutions, no intermediates were observed except traces of sulfite at pH 9. The faster rate of oxidation in Fe(III)-saturated solutions supports a reaction mechanism in which Fe(III) is the direct oxidant of pyrite in both aerobic and anaerobic systems. The proposal of this mechanism is also supported by theoretical considerations regarding the low probability of a direct reaction between paramagnetic molecular oxygen and diamagnetic pyrite. Results from a study of sphalerite oxidation support the hypothesis that thiosulfate is a key intermediate in sulfate production, regardless of the bonding structure of the sulfide mineral.     

Formation of black carbon-like and alicyclic aliphatic compounds by hydroxyl radical initiated degradation of lignin

Exposure of lignin-derived organic matter (OM) to hydroxyl radicals originating from Fenton type reactions generates condensed aromatic and alicyclic aliphatic compounds, as shown using ultrahigh resolution mass spectrometry. Although condensed aromatic compounds are common in soil and dissolved OM, their presence has been attributed largely to combustion. A non-pyrogenic route for the formation of condensed aromatic compounds from lignin is suggested here, specifically that hydroxyl radical-initiated oxidation of lignin is capable of producing black carbon-like condensed aromatic compounds. Alicyclic aliphatic compounds are also produced, likely as part of a concerted process involving ring opening, polymerization and/or cyclization and hydrogen abstraction. Hydroxyl radicals associated with lignin degradation are produced through photochemistry in aqueous systems and enzymatic microbial processes in soil.     

Pyrite oxidation inhibition by a cross-linked lipid coating

The effect of a diacetylene-containing phospholipid on the oxidation of pyrite, FeS₂, was investigated. Earlier work reported by our research group showed that the adsorption of l,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine on pyrite suppressed the extent of its oxidation by about 75% over a specific time period. Results presented here show that the pre-exposure to UV radiation of this lipid after sorption onto pyrite results in a 90% suppression. Attenuated total reflection (ATR) Fourier transform infra-red spectroscopy (FTIR) suggests that the UV irradiation of the lipid does not result in degradation of the adsorbed layer. It is believed that the UV exposure results in the cross-linking and polymerization of the adsorbed phospholipid into a relatively impermeable barrier that separates the pyrite from the aqueous phase. The results of this study might have implications for the protection of pyrite from oxidation in the environment.     

Treatment of oily sludge by advanced oxidation process

For treating oily sludge, wet peroxide oxidation (WPO) and catalytic wet oxidation (CWO) were investigated. The CWO experiment was carried out in a 0.5?L batch reactor using FeCl₃ as catalyst. By using WPO, the effects of reaction parameters such as residence time, temperature, H₂O₂ excess, and initial COD were investigated. The results demonstrated that >80?% chemical oxygen demand (COD) was removed by CWO and >90?% COD was removed by WPO. Significantly, more of COD could be removed from the oily sludge by adding H₂O₂ in small doses. In conclusion, WPO was much more effective in the removal of organic compounds from oily sludge.     

Soil alteration by continued oxidation of pyrite tailings

This work examines the alteration processes triggered after the oxidation of pyrite tailings deposited for 3 years over a carbonate soil. The infiltration of the acidic solution into the soil is causing important morphological, compositional and mineralogical changes in the profile. After 3 years of continued action of such alteration, a considerable degradation of the main soil properties was evident, the most notable being the decline in the cation-exchange capacity (caused by the decreases in clay and organic matter content), texture variation, greater electrical conductivity (10-fold greater than in unaffected soil), and the appearance of horizons with colorations strongly differing from those of the original soil (a discoloured layer with greyish tonalities in the first 5 mm, followed by a reddish-brown layer to a depth of 65–70 mm). At the same time, the carbonates have weathered, disappearing completely from the upper 35 mm and partially to 80 mm in depth. There has also been an intense acidification of the soil (with pH values close to 2.0 within the greyish layer) as well as a partial hydrolysis of the primary silicates (mainly feldspars and phyllosilicates), causing extreme infertility of the soil. The resulting products in this process give rise to intense neoformation of gypsum and hydroxysulphates of Fe and Al, which, together with the acidic conditions of the medium, determine the distribution of the main elements of the soil, both in their total and soluble forms.     

Chemical oxidation of N,N-diethyl-m-toluamide by sulfate radical-based oxidation: kinetics and mechanism of degradation

A study was undertaken in order to understand the kinetics and mechanism of the chemical oxidation of N,N-diethyl-m-toluamide, an insect repellent, by sulfate radical. In this experiment, sulfate radical was generated using peroxymonosulfate with iron(II) and cobalt(II) as activator. The second-order rate constant for the reaction of the sulfate radical with N,N-diethyl-m-toluamide was found to be (1.9 ± 0.1) × 10⁹ M^?1 s^?1 at pH 7 and a temperature of 25 °C. Experiments for the chemical oxidation of N,N-diethyl-m-toluamide in river water and secondary wastewater revealed that the percentage of the removal of N,N-diethyl-m-toluamide was slightly influenced by the water matrices. However, the selected oxidation systems are not effective for the removal of N,N-diethyl-m-toluamide in seawater. Transformation by-products of N,N-diethyl-m-toluamide generated using peroxymonosulfate/iron(II) sulfate, peroxymonosulfate/iron(II) chloride, peroxymonosulfate/cobalt(II) sulfate and peroxymonosulfate/cobalt(II) chloride systems were identified. The results indicated that there are slight differences in the distributions of the transformation by-products detected depending on the activator. The common transformation by-products detected in all selected oxidation systems are N,N-diethylbenzamide, N-ethyl-m-toluamide, N,N-dimethyl-m-toluamide, N-ethyl-N-acetyl-m-toluamide, 2-(diethylamino)-1-m-tolylethanone, monohydroxylated N-ethyl-m-toluamide, and dihydroxylated N,N-diethyl-m-toluamide. Monohydroxylated N,N-diethyl-m-toluamide were detected only when the peroxymonosulfate/iron(II) system was applied. For the peroxymonosulfate/cobalt(II) systems, additional isomers of monohydroxylated N-ethyl-m-toluamide were detected. Peroxymonosulfate/cobalt(II) also transformed 2-(diethylamino)-1-m-tolylethanone into N-ethyl-N-(2-oxo-2-m-tolylethyl)acetamide and monohydroxylated 2-(ethyl(vinyl)amino)-1-m-tolylethanone as transformation by-products.     

Sulfide oxidation in brown coal overburden and chemical modeling of reactions in aquifers influenced by sulfide oxidation

With a mean annual flow of 5.9×10¹¹m³yr^–1 and sediment load of 1600x10¹²gyr^–1 the Ganges river ranks second and third, respectively, in terms of water flow and sediment load among the world's rivers. Considering the enormous sediment transport by Ganges to the Bay of Bengal, a study was conducted on the size distribution and mineral characteristics of the suspended sediments of the Ganges river and is reported here. Most of the sediment load has a size range between <4–5.75 ). The sediments are mostly medium to coarse silt and are poorly sorted. Mica dominates among the clay minerals, followed by chlorite, vermiculite, kaolinite, and smectite. Due to differences in geology, smectite becomes a major clay mineral in downstream rivers. At Calcutta, the clay mineral transport in millions of tons per year is 18,464, 8000, and 2147, for mica, smectite, and chlorite, respectively.     

Experimental study of magmatic melt oxidation by CO2

The process of CO₂ flashing through hydrous albite-hedenbergite melt was experimentally examined at a temperature of 1100°C and a pressure of 2 kbar. Carbon dioxide was generated when the melt interacted with calcite, and wollastonite was the predominant synthesized phase. Mafic components were introduced into the hydrous albite melt via the dissolution of natural hedenbergite. Raman spectroscopic data on bubbles of the fluid phase in the quench glass indicate that the CO₂/H₂O proportions of the bubbles vary. IR spectroscopic data on the glass prove that the water concentration after CO₂ flashing decreased from 5.5 to approximately 3 wt %. The comparison of the composition of the recrystallized clinopyroxene in contact with melt (with and without CO₂ blowing) indicates that CO₂ oxidizes Fe in the melt. The redox effect of CO₂ is quantified by the empirical clinopyroxene tool for metering oxygen fugacity (oxometer), which was calibrated based on experimental data. The oxygen fugacity in our experiments with CO₂ flashing (estimated by the clinopyroxene oxometer) was NNO + (3.0?C3.5). Our estimates with the application of the clinopyroxene oxometer indicate that the maximum oxygen fugacity in the magmatic chambers of Vesuvius and Stromboli volcanoes (which are bubbled with CO₂) is also close to NNO + (3.5 ± 0.5).     

Phenylalanine as a hydroxyl radical-specific probe in pyrite slurries

The abundant iron sulfide mineral pyrite has been shown to catalytically produce hydrogen peroxide (H₂O₂) and hydroxyl radical ( ^. OH) in slurries of oxygenated water. Understanding the formation and fate of these reactive oxygen species is important to biological and ecological systems as exposure can lead to deleterious health effects, but also environmental engineering during the optimization of remediation approaches for possible treatment of contaminated waste streams. This study presents the use of the amino acid phenylalanine (Phe) to monitor the kinetics of pyrite-induced ^. OH formation through rates of hydroxylation forming three isomers of tyrosine (Tyr) - ortho-, meta-, and para-Tyr. Results indicate that about 50% of the Phe loss results in Tyr formation, and that these products further react with ^. OH at rates comparable to Phe. The overall loss of Phe appeared to be pseudo first-order in [Phe] as a function of time, but for the first time it is shown that initial rates were much less than first-order as a function of initial substrate concentration, [Phe]_o. These results can be rationalized by considering that the effective concentration of ^. OH in solution is lower at a higher level of reactant and that an increasing fraction of ^. OH is consumed by Phe-degradation products as a function of time. A simplified first-order model was created to describe Phe loss in pyrite slurries which incorporates the [Phe]_o, a first-order dependence on pyrite surface area, the assumption that all Phe degradation products compete equally for the limited supply of highly reactive ^. OH, and a flux that is related to the release of H₂O₂ from the pyrite surface (a result of the incomplete reduction of oxygen at the pyrite surface). An empirically derived rate constant, K _pyr , was introduced to describe a variable ^. OH-reactivity for different batches of pyrite. Both the simplified first-order kinetic model, and a more detailed numerical simulation, yielded results that compare well to the observed kinetic data describing the effects of variations in concentrations of both initial Phe and pyrite. This work supports the use of Phe as a useful probe to assess the formation of ^. OH in the presence of pyrite, and its possible utility for similar applications with other minerals.     

Sphalerite oxidation pathways detected by oxygen and sulfur isotope studies

Sphalerite oxidation is a common process under acid-mine drainage (AMD) conditions and results in the release of , Zn and potentially toxic trace metals, which can pollute rivers and oceans. However, there are only a few studies on the mechanisms of aerobic sphalerite oxidation. Oxygen and S isotope investigations of the produced may contribute to the understanding of sphalerite oxidation mechanisms so helping to interpret field data from AMD sites. Therefore, batch oxidation experiments with an Fe-rich sphalerite were performed under aerobic abiotic conditions at different initial pH values (2 and 6) for different lengths of time (2–100 days). The O and S isotope composition of the produced indicated changing oxidation pathways during the experiments. During the first 20 days of the experiments at both initial pH values, molecular O₂ was the exclusive O source of . Furthermore, the lack of S isotope enrichment processes between and sphalerite indicated that O₂ was the electron acceptor from sphalerite S. As the oxidation proceeded, a sufficient amount of released Fe(II) was oxidized to Fe(III) by O₂. Therefore, electrons could be transferred from sphalerite S sites to adsorbed hydrous Fe(III) and O from the hydration sphere of Fe was incorporated into the produced as indicated by decreasing δ¹⁸O_SO4 values which became more similar to the δ¹⁸O_H2O values. The enrichment of ³²S in relative to the sphalerite may also result from sphalerite oxidation by Fe(III).The incorporation of O₂ into during the oxidation of sphalerite was associated with an O isotope enrichment factor ε_SO4–O2 of ca. −22‰. The O isotope enrichment factor ε_SO4–H2O was determined to be ?4.1‰. A comparison with O and S studies of other sulfides suggests that there is no general oxidation mechanism for acid-soluble sulfides.     

含钒金红石可见光下催化降解亚甲基蓝实验研究

利用含有钒等杂质的金红石可部分吸收可见光的特性,以500 W卤素灯作为光源,实验研究了其对亚甲基蓝的可见光催化降解,结果表明,该金红石具有催化活性,7 h后亚甲基蓝可降解71 2%。经过加热、粉碎改性方法处理后的金红石光催化活性明显提高,加热1 100 ℃的金红石样品7 h后可使亚甲基蓝的降解率达到90 4%。增加光照强度、加入适当的H2O2 都可提高降解效果。实验为充分开发利用天然金红石提出了新的途径,为环境污染治理提出了新方法。     

Pyrite-induced hydroxyl radical formation and its effect on nucleic acids

Background  

Pyrite, the most abundant metal sulphide on Earth, is known to spontaneously form hydrogen peroxide when exposed to water. In this study the hypothesis that pyrite-induced hydrogen peroxide is transformed to hydroxyl radicals is tested.     

主要铁氧化物催化H2O2 氧化地下水中硝基苯实验

实验研究了含水层介质中主要铁氧化物催化H2O2 氧化地下水中硝基苯的机理和主要影响因素,为硝基苯污染地下水的原位化学修复技术提供了一定的理论依据。实验模拟在地下环境温度8 ℃ ～ 10 ℃条件下,利用动力学方程对硝基苯的衰减进行拟合,结果表明,其衰减系数K = 0. 044 3 min － 1 ; 硝基苯与H2O2 的最佳摩尔比为1∶200; 主要铁氧化物催化H2O2 氧化硝基苯能力依次为: 磁铁矿＞ 针铁矿＞ 氢氧化铁＞ 赤铁矿。