A study of the applicability of various activated persulfate processes for the treatment of 2,4-dichlorophenoxyacetic acid

This paper reports an investigation of different persulfate (PS) activations, including PS at 20 °C (PS), thermally activated PS at 70 °C (T-PS), ferrous-ion activated PS at 20 °C [Fe(II)-PS)], hydrogen peroxide activated PS at 20 °C, and sodium hydroxide activated PS at 20 °C, for degradation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous phase. Several findings were made in this study including the followings: the 2,4-D degradation rates in T-PS and Fe(II)-PS systems were higher than other systems. However, complete degradation of 2,4-D and associated derivatives can be reached in all oxidation systems, with various reaction times. When considering the results of PS consumption during the 48 h reaction time to reach complete 2,4-D degradation, the T-PS system consumed all of the PS while only 10 % of the PS was consumed in the Fe(II)-PS system. The evaluation of optimum PS and ferrous ion doses indicated that under a fixed initial PS concentration, increasing Fe²⁺ concentration generally increased the amount of initial rapid degradation of 2,4-D and dissolved organic carbon. However, the effectiveness of the Fe(II)-PS system may be inhibited by the presence of excess iron. When a fixed level of Fe²⁺ was employed, various PS concentrations resulted in approximately equal 2,4-D degradation. The Fe(II)-PS system was found to be sensitive to the initial Fe²⁺ concentration, and the presence of soil revealed minor influence on the 2,4-D degradation by the Fe(II)-PS system. These findings indicate that the iron-activated PS process may be an effective method for remediating 2,4-D contamination.     

Effect of Fe2+ amendment on photodegradation kinetics of imidacloprid in moist soil

The present study deals with the effect of Fe²⁺ on degradation kinetics of imidacloprid in moist soil under UV system. The moist soil samples were spiked with imidacloprid and irradiated in specially designed UV-photoreactor. The analysis of imidacloprid was carried out by using HPLC–DAD system. UV irradiation caused about ten fold increase in photodegradation rate of the pesticide. Amendment of soil with Fe²⁺ at concentrations of 30 mg/kg led to a further increase in the rate of photodegradation, i.e., a 98 % degradation of imidacloprid was observed in the presence of iron after 32 days of irradiation. Moreover, the half-life of imidacloprid in Fe²⁺ -amended soil was observed to be reduced to 7 days that in the absence of Fe²⁺ was recorded to be 21 days. Iron was also observed to affect the half-life of imidacloprid in dark. When compared with unsterilized Fe²⁺-amended batch treatments, the t _1/2 in sterilized Fe²⁺-amended batch treatments increased from 58 to 96 days. Imidacloprid-urea was detected by HPLC as the only stable photodegradation byproduct of imidacloprid in the soil.     

Removal of acetaminophen from hospital wastewater using electro-Fenton process

The current work deals with efficient removal of acetaminophen (AC) from hospital wastewater using electro-Fenton (EF) process. The degradation yield of 99.5% was obtained under optimal experimental conditions, namely 5.75 mg L^?1 initial AC concentration, 2.75 pH solution, 3-cm inter-electrode distance, 100 mg L^?1 KCl electrolyte, 122.5 µL L^?1 H₂O₂, 8 mA cm^?2 current density at equilibrium time of 8 min. Analysis of variance (ANOVA) suggested that the effect of mentioned operating parameters was statistically significant on the AC removal. The low probability amount of P value (P < 0.0001), the Fisher’s F-value of 65.91, and correlation coefficient of the model (R² = 0.9545) revealed a satisfactory correlation between the experimental and the predicted values of AC removal. The predicted removal efficiency of 99.4% was in satisfactory agreement with the obtained experimental removal efficiency of 98.7%. The AC degradation during the EF followed a first-order kinetic model with rate constants (K_app) of 0.6718 min^?1. Using the ordinary radical scavengers revealed that main mechanism of AC degradation controlled by the hydroxyl free radicals produced throughout the EF process. The excess amount of iron (II) scavenged the active radicals and diminished the concentration of ^·OH available to react with AC. The optimum molar ratio of H₂O₂ to Fe²⁺ was found to be 2.5. The developed EF process as a promising technique applied for treatment of real samples.     

<Superscript>57</Superscript>Fe Mössbauer spectroscopy,X-ray single-crystal diffractometry,and electronic structure calculations on natural sinhalites

Natural sinhalites, MgAlBO_4, from the Ratnapura District, Sri Lanka, and from Bodnar Quarry near Hamburg, Sussex Co., New Jersey, USA, have been characterized by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe, X-ray single-crystal diffractometry and by electronic structure calculations in order to determine the oxidation state and site occupancy of iron in the sinhalite structure. The samples contain about 3.35 and 1.46 wt% of total iron oxide, respectively. The structure refinement is successful and reproduces the total iron content provided that the substitution of Mg²⁺ by Fe²⁺ on the M2 position only is assumed. The ⁵⁷Fe Mössbauer spectra at 77, 293, 573 and 773 K can be resolved into two doublets with hyperfine parameters common for octahedrally coordinated high-spin Fe²⁺. There is no evidence for iron in the tetrahedral site. Electronic structure calculations in local spin density approximation yield hyperfine parameters for Fe²⁺ on the M2-site at 0, 293, 573 and 773 K in quantitative agreement with experiments. Calculated spectroscopic properties for Fe²⁺ on the M1-site are at variance with the experimental data and, thus, indicate that substitution of Al³⁺ by Fe²⁺, if occurring at all, must be accompanied by considerable local expansion and distortion of the M1-octahedron.     

Comparison of UV-C irradiation,ozonation, and iron chelates treatments for degradation of tetracycline in water

The objective of this study was to propose a method for efficient degradation of tetracycline as a water contaminant. UV-C rays, ozonation, and iron chelates were used for removal of tetracycline from water. Aqueous solution of tetracycline (5 × 10^?5 M) was exposed to UV-C rays (in two doses—6 and 12 W), ozonation (at 6–12 mg ozone), or iron chelates: iron(III) sodium ethylenediaminetetraacetate, iron(III) trisglycinate, and iron(III) citrate. For each of iron compounds, three doses were studied: 2.5 × 10^?5 M, 5 × 10^?5 M, 10 × 10^?5 M. The experiments have shown that aqueous solution of tetracycline (5 × 10^?5 M) is immediately degraded as a result of ozonation with 12 mg ozone. Absorbance of tetracycline decreased from A = 0.78 to A = 0.35 after 20-min ozone treatment of sample. The fluorescence spectra revealed the presence of two ozone-induced TC degradation products with fluorescence maxima at 523 and 531 nm appearing immediately after the ozonation treatment. On the other hand, iron(III) sodium ethylenediaminetetraacetate and iron(III) trisglycinate gave rise to a single TC degradation product with a fluorescence maximum at 531 nm, observed after 10 days of the experiment. On application of iron(III) trisglycinate, at any studied concentration, tetracycline becomes degraded faster—in 4 days. Iron(III) citrate degraded 90 % of tetracycline, when used at the level 10 × 10^?5 M. The biggest changes in tetracycline concentration were obtained as a result of ozonation and iron(III) citrate treatments.     

Pressure effect on the electronic structure of iron in (Mg,Fe)(Si,Al)O3 perovskite: a combined synchrotron Mössbauer and X-ray emission spectroscopy study up to 100 GPa

We investigated the valence state and spin state of iron in an Al-bearing ferromagnesian silicate perovskite sample with the composition (Mg_0.88Fe_0.09)(Si_0.94Al_0.10)O₃ between 1 bar and 100 GPa and at 300 K, using diamond cells and synchrotron Mössbauer spectroscopy techniques. At pressures below 12 GPa, our Mössbauer spectra can be sufficiently fitted by a “two-doublet” model, which assumes one ferrous Fe²⁺-like site and one ferric Fe³⁺-like site with distinct hyperfine parameters. The simplest interpretation that is consistent with both the Mössbauer data and previous X-ray emission data on the same sample is that the Fe²⁺-like site is high-spin Fe²⁺, and the Fe³⁺-like site is high-spin Fe³⁺. At 12 GPa and higher pressures, a “three-doublet” model is necessary and sufficient to fit the Mössbauer spectra. This model assumes two Fe²⁺-like sites and one Fe³⁺-like site distinguished by their hyperfine parameters. Between 12 and 20 GPa, the fraction of the Fe³⁺-like site, Fe³⁺/∑Fe, changes abruptly from about 50 to 70%, possibly due to a spin crossover in six-coordinate Fe²⁺. At pressures above 20 GPa, the fractions of all three sites remain unchanged to the highest pressure, indicating a fixed valence state of iron within this pressure range. From 20 to 100 GPa, the isomer shift between the Fe³⁺-like and Fe²⁺-like sites increases slightly, while the values and widths of the quadruple splitting of all three sites remain essentially constant. In conjunction with the previous X-ray emission data, the Mössbauer data suggest that Fe²⁺ alone, or concurrently with Fe³⁺, undergoes pressure-induced spin crossover between 20 and 100 GPa.     

Degradation of dimethyl sulfoxide through fluidized-bed Fenton process: kinetic analysis

In this study, fluidized-bed Fenton process (FBF) was used to degrade dimethyl sulfoxide (DMSO), one of the most widely used solvents. Oxidation by Fenton’s reagent, Fe⁺² and H₂O₂, is one of the cheapest advanced oxidation processes due to the high availability of the reagents. FBF is a modified approach that reduces the large amount of iron oxide sludge formed in conventional Fenton process. The optimal treatment efficiencies by FBF with 2 h of reaction were 95.22 % of DMSO degradation and 34.38 % of COD removal at the conditions of 5 mM DMSO, 68.97 g/L SiO₂ carrier, pH_initial 3.0, 5 mM Fe²⁺, and 32.5 mM H₂O₂. The kinetic study was also done to investigate the two stages involved in the oxidation. The first stage fitted the zero reaction order with overall initial rate’s apparent rate constant, k ₁, of ?0.099. The second stage fitted the first order of DMSO degradation, with rate constant, k ₂, of ?0.0005.     

Fe~(2+)活化过硫酸盐在石油污染土壤中修复实验研究

硫酸根自由基的高级氧化技术以高效率、污染少等优点被广泛用于环境污染治理。本文以实际石油污染土壤为对象,运用该体系对土壤进行修复研究,分别从Na_2S_2O_8/Fe~(2+)摩尔比、体系pH值、Na_2S_2O_8/Fe~(2+)投加量等方面开展了实验研究。实验表明:当Na_2S_2O_8/Fe2+摩尔比为2∶3时,石油污染物的降解效果最好,体系的pH值对降解效果影响不大,1 g土壤中浓度为0.1 mol/L的过硫酸钠和硫酸亚铁溶液的最佳加入量为2 m L、3 m L时,对土壤的降解效果最为明显,故每吨污染土壤的添加量大约为2×10~6m L、3×10~6m L。     

The diagenetic geochemistry and contamination assessment of iron,cadmium, and lead in the sediments from the Shuangtaizi estuary,China

Sediment and pore water samples have been collected from the coastal tidal flat in the Shuangtaizi estuary, China, in order to investigate the geochemical behavior of iron, cadmium, and lead during diagenesis and to assess the degree of contamination. The calculated enrichment factors and geoaccumulation indices for separate elements show that anthropogenic activities have had no significant influence on the distribution of Fe and Pb in the study area, whereas the distribution of Cd has been closely influenced in this way. The high percentage of exchangeable Cd (average of 56.34%) suggests that Cd represents a potential hazard to benthic organisms in the estuary. The calculated diffusive fluxes of metals show that the most mobilized metal is Fe (9.22 mg m^?2 a^?1), followed by Cd (0.54 mg m^?2 a^?1) and Pb (0.42 mg m^?2 a^?1). Low Fe²⁺ contents in surface pore water, alongside high chromium-reducible sulfur contents, and low acid-volatile sulfur, and elemental sulfur contents at 0–25 cm depth in sediments show that Fe²⁺ is formed by the reduction of Fe oxides and is transformed first to a solid phase of iron monosulfides (FeS) and eventually to pyrite (FeS₂). The release of adsorbed Pb due to reductive dissolution of Fe/Mn oxides during early diagenesis could be a source of Pb²⁺ in pore water. From the relatively low total organic carbon contents measured in sediments (0.46–1.28%, with an average of 0.94%) and the vertical variation of Cd²⁺ in pore water, sulfide or Fe/Mn oxides (instead of organic matter) are presumed to exert a significant influence on carrying or releasing Cd by the sediments.     

Catalytic ozonation of dimethyl phthalate by Ce-substituted goethite

Dimethyl phthalate (DMP) is ubiquitous in aquatic environments due to extensively used as plasticizer, which has received increasing attention in recent years. In this study, the catalytic ozonation of dimethyl phthalate was performed using Ce-substituted goethite as a novel catalyst, which was prepared by isomorphous substitution method. The specific surface area, pHpzc and surface hydroxyl density of the catalyst were determined. The catalyst was characterized using X-ray diffraction, scanning electron microscope and Fourier transform infrared spectroscopy. The removal efficiency of DMP was almost 100% after 30 min, and about 40% DMP was mineralized after 60 min, which was nearly four times higher than single ozonation. During catalytic ozonation process, anions (PO₄ ^3?, SO₄ ^2?, Cl^?) affected DMP degradation, indicating that surface hydroxyl groups on the surface of catalyst were main active sites. The electron transfer process by redox reaction between Ce³⁺/Ce⁴⁺, Fe²⁺/Fe³⁺ was proposed, and their interaction could also promote the formation of hydroxyl radicals. Ce-substituted goethite was an efficient catalyst for degradation of DMP by catalytic ozonation.     

Electronic state of Fe2+ in (Mg,Fe)(Si,Al)O3 perovskite and (Mg,Fe)SiO3 majorite at pressures up to 81 GPa and temperatures up to 800 K

Despite a large number of studies of iron spin state in silicate perovskite at high pressure and high temperature, there is still disagreement regarding the type and P–T conditions of the transition, and whether Fe²⁺ or Fe³⁺ or both iron cations are involved. Recently, our group published results of a Mössbauer spectroscopy study of the iron behaviour in (Mg,Fe)(Si,Al)O₃ perovskite at pressures up to 110 GPa (McCammon et al. 2008), where we suggested stabilization of the intermediate spin state for 8- to 12-fold coordinated ferrous iron (^[8–12]Fe²⁺) in silicate perovskite above 30 GPa. In order to explore the behaviour in related systems, we performed a comparative Mössbauer spectroscopic study of silicate perovskite (Fe_0.12Mg_0.88SiO₃) and majorite (with two compositions—Fe_0.18Mg_0.82SiO₃ and Fe_0.11Mg_0.88SiO₃) at pressures up to 81 GPa in the temperature range 296–800 K, which was mainly motivated by the fact that the oxygen environment of ferrous iron in majorite is quite similar to that in silicate perovskite. The ^[8–12]Fe²⁺ component, dominating the Mössbauer spectra of majorites, shows high quadrupole splitting (QS) values, about 3.6 mm s^?1, in the entire studied P–T region (pressures to 58 GPa and 296–800 K). Decrease of the QS of this component with temperature at constant pressure can be described by the Huggins model with the energy splitting between low-energy e _g levels of ^[8–12]Fe²⁺ equal to 1,500 (50) cm^?1 for Fe_0.18Mg_0.82SiO₃ and to 1,680 (70) cm^?1 for Fe_0.11Mg_0.88SiO₃. In contrast, for the silicate perovskite dominating Mössbauer component associated with ^[8–12]Fe²⁺ suggests the gradual change of the electronic properties. Namely, an additional spectral component with central shift close to that for high-spin ^[8–12]Fe²⁺ and QS about 3.7 mm s^?1 appeared at ~35 (2) GPa, and the amount of the component increases with both pressure and temperature. The temperature dependence of QS of the component cannot be described in the framework of the Huggins model. Observed differences in the high-pressure high-temperature behaviour of ^[8–12]Fe²⁺ in the silicate perovskite and majorite phases provide additional arguments in favour of the gradual high-spin—intermediate-spin crossover in lower mantle perovskite, previously reported by McCammon et al. (2008) and Lin et al. (2008).     

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.     

Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods

A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe²⁺ at M1 as well as at M2, and in a first approach assigned Fe³⁺ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε _i,tot = 65,000 ± 3,000 lmol_H2O ^?1 cm^?2. Using this new ε _i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H₂O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe³⁺ (<0.1 Fe³⁺ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm^?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al³⁺ at the tetrahedral site (OH bands around 3,525 cm^?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe³⁺-rich sample (0.2 Fe³⁺ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm^?1 plus shoulder at 3,450 cm^?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe³⁺ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe²⁺ and combined with increase in Fe³⁺. That dehydration is correlated with oxidation of Fe²⁺ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH^? content and giving no indication of Fe²⁺-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe²⁺ at M2 and low-water concentrations, i.e., at a ratio of Fe^{2+ M2}/H > 10 dehydration occurs by iron oxidation of Fe²⁺ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe²⁺ at M2 but high-water concentrations, i.e., ratio of Fe^{2+ M2}/H < 5.0 dehydration occurs through oxidation of Fe²⁺ at M1.     

Iron Reduction Along an Inundation Gradient in a Tidal Sedge (<Emphasis Type="Italic">Cyperus malaccensis</Emphasis>) Marsh: the Rates,Pathways, and Contributions to Anaerobic Organic Matter Mineralization

Incubation experiments were adopted to characterize the rates and pathways of iron reduction and the contributions to anaerobic organic matter mineralization in the upper 0–5 cm of sediments along a landscape-scale inundation gradient in tidal marsh sediments in the Min River Estuary, Southeast China. Similar sediment characteristics, single-species vegetation, varied biomass and bioturbation, distinct porewater pH, redox potential, and electrical conductivity values have resulted in a unique ecogeochemical zonation along the inundation gradient. Decreases in solid-phase Fe(III) and increases in nonsulfidic Fe(II) and iron sulfide were observed in a seaward direction. Porewater Fe²⁺ was only detected in the upland area. High rates of iron reduction were observed in incubation jars, with significant accumulations of nonsulfidic Fe(II), moderate accumulations of iron sulfides, and negligible accumulations of porewater Fe²⁺. Most of the iron reduction was microbially mediated rather than coupled to reduced sulfides. Microbial iron reduction accounted for 20–89 % of the anaerobic organic matter mineralization along the inundation gradient. The rate and dominance of microbial iron reduction generally decreased in a seaward direction. The contributions of microbial iron reduction to anaerobic organic matter mineralization depended on the concentrations of bioavailable Fe(III), the spatial distribution of which was significantly related to tidal inundation. Our results clearly showed that microbial iron reduction in the upper sediments along the gradient is highly dependent on spatial scales controlled primarily by tidal inundation.     

Fe sorption onto nontronite (NAu-2)

The sorption of ferrous iron to a clay mineral, nontronite (NAu-2, a ferruginous smectite), was investigated under strictly anoxic conditions as a function of pH (3-10), Fe²⁺ concentration (0.01-50 mM), equilibration time (1-35 days), and ionic strength (0.01-0.5 M NaClO₄). The surface properties of NAu-2 were independently characterized to determine its fixed charge and amphoteric site density in order to interpret the Fe²⁺ sorption data. Fe²⁺ sorption to NAu-2 was strongly dependent on pH and ionic strength, reflecting the coupled effects of Fe²⁺ sorption through ion exchange and surface complexation reactions. Fe²⁺ sorption to NAu-2 increased with increasing pH from pH 2.5 to 4.5, remained constant from pH 4.5 to 7.0, increased again with further increase of pH from pH 7.0 to 8.5, and reached a maximum above pH 8.5. The Fe²⁺ sorption below pH 7.0 increased with decreasing ionic strength. The differences of Fe²⁺ sorption at different ionic strengths, however, diminished with increasing equilibration time. The Fe²⁺ sorption from pH 4.5 to 7.0 increased with increasing equilibration time up to 35 days and showed stronger kinetic behavior in higher ionic strength solutions. The kinetic uptake of Fe²⁺ onto NAu-2 is consistent with a surface precipitation mechanism although our measurements were not able to identify secondary precipitates. An equilibrium model that integrates ion exchange, surface complexation and aqueous speciation reactions reasonably well describes the Fe²⁺ sorption data as a function of pH, ionic strength, and Fe²⁺ concentration measured at 24 h of equilibration. Model calculations show that the species Fe(OH)⁺ was required to describe Fe²⁺ sorption above pH 8.0 satisfactorily. Overall, this study demonstrated that Fe²⁺ sorption to NAu-2 is affected by complex equilibrium and kinetic processes, likely caused by surface precipitation reactions.     

二价铁活化过硫酸盐去除水中苯胺

零价铁和硝基苯反应后生成二价铁和苯胺,而苯胺也是地下水污染物。硫酸根自由基具有强氧化性,可以降解苯胺。而二价铁可以活化过硫酸盐产生硫酸根自由基,进而去除苯胺。本文研究了二价铁浓度、过硫酸盐浓度、苯胺初始浓度、体系初始pH、反应温度等因素对二价铁活化过硫酸盐去除水中苯胺处理效率的影响。结果表明:1)Fe2+活化过硫酸盐生成SO-4·能快速并有效氧化降解苯胺,对于目标浓度为1 000 mg/L的苯胺而言,Fe2+浓度为3.3 mmol/L,Na2S2O8浓度为4.4 mmol/L时,对苯胺有较佳降解效果,苯胺的降解率为86.33%。2体系对较低浓度的苯胺降解效果较好,当污染物初始浓度由1 000 mg/L降低到500 mg/L和100 mg/L时,苯胺降解率由86.33%升高为90.27%和97.16%。3初始pH对苯胺的降解率影响较大,中性条件下(pH=7左右)降解率较好,高初始pH(pH=9,11)和低初始pH条件(pH=3,5)下均低于中性条件下苯胺的降解效率。4体系的温度变化对降解率影响不明显。     

Immobilized <Emphasis Type="Italic">β</Emphasis>-lactamase on Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> magnetic nanoparticles for degradation of <Emphasis Type="Italic">β</Emphasis>-lactam antibiotics in wastewater

The emergence of antibiotics residues in pharmaceutical industrial wastewater has been a significant environment problem. However, current methods of treating antibiotic-polluted wastewater are inefficient, of high cost and time-consuming. In this study, highly effective enzymatic Fe₃O₄ magnetic nanoparticles were developed, which is extremely simple and can degrade antibiotics in a fast manner at a low cost. β-Lactamase, a representative enzyme for β-lactam antibiotic degradation, was covalently immobilized on the surface of magnetic nanoparticles modified with amino groups by a simple cross-linking process. The immobilized β-lactamase displayed a wider pH and temperature range for penicillin G degradation than the free enzyme. Meanwhile, the thermostability and storage stability of the immobilized β-lactamase were improved. Fifty milligrams magnetic nanoparticles immobilized with β-lactamase can thoroughly degrade 100 mL penicillin G (5–50 mg L^?1) within 5 min. Even if the β-lactamase immobilized on the nanoparticles was reused 35 times in the 5 mg L^?1 penicillin G solution, it still kept more than 95% degradation efficiency. These suggest that magnetic nanoparticles immobilized with β-lactamase have a sufficient capacity for degrading antibiotics in wastewater and will serve as a practical and economical solution to antibiotic pollution in pharmaceutical industrial wastewater treatment.     

Natural iron-containing blue and colorless euclase studied by electron paramagnetic resonance

Natural blue and colorless rare-gem mineral specimens of euclase from Brazil are investigated by electron paramagnetic resonance (EPR). Angular dependences of Fe³⁺ EPR spectra in three mutually perpendicular crystal planes are analyzed revealing g and D tensors with significant low-symmetry effects, as for example, the high asymmetry parameter E/D = 0.28. Fourth-order degree Stevens parameters are also included in analysis. The anisotropy of both g and D tensors is consistent with Fe³⁺ substituting for Al³⁺ ions in strongly distorted AlO₅(OH) octahedra in which the oxygen distances range from 1.85 to 1.98 Å. Fe³⁺ is not responsible for the blue color because colorless and blue euclase show nearly the same Fe³⁺ concentration as measured by EPR. However, total iron content in blue sample is much higher than in the colorless one suggesting that the existing model that Fe²⁺–Fe³⁺ intervalence charge transfer transition may explain the blue color of euclase.     

Melting of clinopyroxene + magnesite in iron-bearing planetary mantles and implications for the Earth and Mars

The assemblage clinopyroxene + magnesite was observed in Earth’s high-pressure metamorphic samples, and its stability in subducting slabs was confirmed by experiments. Recent studies also suggested that the fO₂ variations observed in SNC meteorites can be explained by polybaric graphite-CO-CO₂ equilibria in the Martian mantle. Although there is no direct evidence for the stability of the cpx + mc assemblage in Mars mantle, its high-pressure–high-temperature decomposition to cpx + fo + CO₂ makes it a good analogue for the source of carbon metasomatism, in particular, to study nakhlites formation. Iron, which is present in the Earth’s and Martian mantles, may, however, influence the speciation of carbon. We performed experiments on a clinopyroxene + magnesite assemblage at 1.8 and 3.0 GPa and temperatures corresponding to the Earth’s and Martian mantles. The role of iron and of fO₂ was investigated by (1) replacing all or part of the magnesite by siderite FeCO₃, (2) adding Fe⁰ and (3) using graphite C capsules. A carbonate-silicate melt forms at both Earth and Mars conditions. Clinopyroxene and olivine are the main solid phases in the iron-free experiments. Fe²⁺ and Fe⁰ decrease their melting temperatures and increase the silicate fraction in the melt. The produced carbonate-silicate melts may be involved in the formation of some carbon-rich lavas on Earth (e.g., carbonatites, ultramafic lamprophyres, or kamafugites). Our results may also be used to interpret ophiolite samples or inclusions. In particular, we show that wüstite may form in equilibrium with carbonate-silicate melt in opx-(and silica-) poor regions of the mantle below 3 GPa. Our results also confirm the hypothesis of carbon metasomatism in the Martian nakhlites source. Immiscibility or reduction could explain the absence or rarity of C in Martian lavas.