Additional OH Research Articles

Detailed, sterically-resolved modeling of soot oxidation: Role of O atoms, interplay with particle nanostructure, and emergence of inner particle burning

A newly-developed detailed mechanism of soot oxidation was tested against experimental observations. The computations were performed at an atomistic level and with a detailed consideration of soot particle surface sites. Several additional reactions were investigated theoretically and one of them, oxidation of embedded five-member rings by O atoms, was included in the model. The primary focus of the study was on the high-temperature shock-tube experiments of Roth et al. (1991). The reaction model was able to reproduce the experimental results, but required coupling to particle nanostructure: partial oxidation of PAH molecules and the decrease in PAH initial sizes along the oxidation path. The principle reaction mechanism was identified to be the formation of oxyradicals, their decomposition, formation of hard-to-oxidize embedded five-member rings, and oxidation of the latter predominantly by O atoms. The analysis identified O as the most effective oxidizer of the embedded five-member rings, which thus controls the rate of the overall oxidation. The model thus predicts fast oxidation during a brief initial period followed by a slow-oxidation one. The model of partial oxidation of an aromatic molecule and switching to the next intact molecule suggests pore formation and subsequent inner particle burning. We also investigated the ability of the present model to reproduce recent measurements of soot oxidation rates performed by Camacho et al. (2015) at about 1000 K. The initial reaction model failed to predict these results, and no adjustment could reconcile the differences. The only way to bring the model to experimental values was by assuming a catalytic decomposition of water on the reactor wall supplying additional radicals, H and OH, to the reacting gas mixture. Additional chemistry, oxidation through complex formation at neighboring surface sites, was required to fully reproduce the experimental observations. These additional reactions were found to play no role in the high-temperature simulations, nor were they sufficient to reproduce the low-temperature experiment on their own, without the assumed catalytic decomposition of water.

Preparation and photo Fenton-like activities of high crystalline CuO fibers

CuO fibers were successfully fabricated by a simple electrospinning method, followed by calcination. Some experimental parameters such as the content of Cu(NO3)2∙3H2O, the content of PVP, the stirring time, the applied voltage, as well the calcination temperature were investigated, respectively, and their influences on the morphologies of fibers and the spinnability of precursor solution were analyzed. The CuO fibers calcined at 550°C consisted of numerous CuO grains exhibited a well-crystalline structure. Furthermore, the CuO fibers demonstrated effective photo-Fenton degradation to methyl orange with the assist of H2O2 and the adding volume of H2O2 affects the degradation activities greatly. The degradation rate of methyl orange by the CuO fibers in the presence of 238.8mmol/L H2O2 is 3.8 times as much as one by P25 alone under the irradiation of Xe lamp. The degradation ratio of methyl orange could achieve 83% in 180min. The enhanced photocatalytic activities of the CuO fibers were attributed to two aspects: one is the well-crystalline of CuO fibers; the other is that H2O2 accepted the photogenerated electrons and holes effectively, which not only prevented the recombination of charge carriers but also produced additional OH. In this work, the formation and photocatalysis mechanisms of CuO fibers were also investigated.

Defect levels and hyperfine constants of hydrogen in beryllium oxide from hybrid-functional calculations and muonium spectroscopy

The atomistic and electronic structures of isolated hydrogen states in BeO were studied by ab initio calculations and muonium spectroscopy (SR). Whereas standard density-functional theory with a semi-local GGA functional led to a detailed probing of all possible minimum-energy configurations of hydrogen further calculations with the hybrid HSE06 functional provided improved properties avoiding band-gap and self-interaction errors. Similarly to earlier findings for the other wide-gap alkaline-earth oxide, MgO, hydrogen in BeO is also predicted to be an amphoteric defect with the pinning level, E(), positioned in the mid-gap region. Both donor and acceptor levels were found too deep in the gap to allow for hydrogen to act as a source of free carriers. Whereas, hydrogen in its positively-charged state, , adopts exclusively hydroxide-bond OH configurations, and instead show a preference to occupy cage-like interstitial sites in the lattice. in particular displays a multitude of minimum-energy configurations: its lowest-energy ground state resembles closely a trapped-atom state with a nearly spherical spin-density profile. In contrast to the strongly ionic MgO, in BeO was further found to stabilise in additional higher-energy elongated-bond OH configurations whose existence should be traced to a partial covalent character of the Be–O bonding. Calculations of the proton-electron hyperfine coupling for all states showed that the ground-state interstitial configuration is dominated by an isotropic hyperfine interaction with a magnitude very close to the vacuum value, a finding corroborated by the SR-spectroscopy data.

Molecular dynamics simulation study of the effect of glycerol dialkyl glycerol tetraether hydroxylation on membrane thermostability

Archaeal tetraether membrane lipids span the whole membrane width and present two C40 isoprenoid chains bound by two glycerol groups (or one glycerol and calditol). These lipids confer stability and maintain the membrane fluidity in mesophile to extremophile environments, making them very attractive for biotechnological applications. The isoprenoid lipid composition in archaeal membranes varies with temperature, which has placed these lipids in the focus of paleo-climatological studies for over a decade. Non-hydroxylated isoprenoid archaeal lipids are typically used as paleo-thermometry proxies, but recently identified hydroxylated (OH) derivatives have also been proposed as temperature proxies. The relative abundance of hydroxylated lipids increases at lower temperatures, but the physiological function of the OH moiety remains unknown. Here we present molecular dynamics simulations of membranes formed by the acyclic glycerol-dialkyl-glycerol-tetraether caldarchaeol (GDGT-0), the most widespread archaeal core lipid, and its mono-hydroxylated variant (OH-GDGT-0) to better understand the physico-chemical properties conferred to the membrane by this additional moiety. The molecular dynamics simulations indicate that the additional OH group forms hydrogen bonds mainly with the sugar moieties of neighbouring lipids and with water molecules, effectively increasing the size of the polar headgroups. The hydroxylation also introduces local disorder that propagates along the entire alkyl chains, resulting in a slightly more fluid membrane. These changes would help to maintain trans-membrane transport in cold environments, explaining why the relative abundance of hydroxylated Archaea lipids increases at lower temperatures. The in silico approach aids to understand the underlying physiological mechanisms behind the hydroxylated lipid based paleo-thermometer recently proposed.

Radical chemistry at a rural site (Wangdu) in the North China Plain: observation and model calculations of OH, HO<sub>2</sub> and RO<sub>2</sub> radicals

Abstract. A comprehensive field campaign was carried out in summer 2014 in Wangdu, located in the North China Plain. A month of continuous OH, HO2 and RO2 measurements was achieved. Observations of radicals by the laser-induced fluorescence (LIF) technique revealed daily maximum concentrations between (5–15) × 106 cm−3, (3–14) × 108 cm−3 and (3–15) × 108 cm−3 for OH, HO2 and RO2, respectively. Measured OH reactivities (inverse OH lifetime) were 10 to 20 s−1 during daytime. The chemical box model RACM 2, including the Leuven isoprene mechanism (LIM), was used to interpret the observed radical concentrations. As in previous field campaigns in China, modeled and measured OH concentrations agree for NO mixing ratios higher than 1 ppbv, but systematic discrepancies are observed in the afternoon for NO mixing ratios of less than 300 pptv (the model–measurement ratio is between 1.4 and 2 in this case). If additional OH recycling equivalent to 100 pptv NO is assumed, the model is capable of reproducing the observed OH, HO2 and RO2 concentrations for conditions of high volatile organic compound (VOC) and low NOx concentrations. For HO2, good agreement is found between modeled and observed concentrations during day and night. In the case of RO2, the agreement between model calculations and measurements is good in the late afternoon when NO concentrations are below 0.3 ppbv. A significant model underprediction of RO2 by a factor of 3 to 5 is found in the morning at NO concentrations higher than 1 ppbv, which can be explained by a missing RO2 source of 2 ppbv h−1. As a consequence, the model underpredicts the photochemical net ozone production by 20 ppbv per day, which is a significant portion of the daily integrated ozone production (110 ppbv) derived from the measured HO2 and RO2. The additional RO2 production from the photolysis of ClNO2 and missing reactivity can explain about 10 % and 20 % of the discrepancy, respectively. The underprediction of the photochemical ozone production at high NOx found in this study is consistent with the results from other field campaigns in urban environments, which underlines the need for better understanding of the peroxy radical chemistry for high NOx conditions.

Ortho and para chromophores of green fluorescent protein: controlling electron emission and internal conversion.

Green fluorescent protein (GFP) continues to play an important role in the biological and biochemical sciences as an efficient fluorescent probe and is also known to undergo light-induced redox transformations. Here, we employ photoelectron spectroscopy and quantum chemistry calculations to investigate how the phenoxide moiety controls the competition between electron emission and internal conversion in the isolated GFP chromophore anion, following photoexcitation with ultraviolet light in the range 400-230 nm. We find that moving the phenoxide group from the para position to the ortho position enhances internal conversion back to the ground electronic state but that adding an additional OH group to the para chromophore, at the ortho position, impedes internal conversion. Guided by quantum chemistry calculations, we interpret these observations in terms of torsions around the C-C-C bridge being enhanced by electrostatic repulsions or impeded by the formation of a hydrogen-bonded seven-membered ring. We also find that moving the phenoxide group from the para position to the ortho position reduces the energy required for detachment processes, whereas adding an additional OH group to the para chromophore at the ortho position increases the energy required for detachment processes. These results have potential applications in tuning light-induced redox processes of this biologically and technologically important fluorescent protein.

Theoretically derived mechanisms of HPALD photolysis in isoprene oxidation.

In this work we identified and theoretically quantified two photolysis mechanisms of HPALDs (hydroperoxy aldehydes) that result from the isomerization of peroxy radicals in the atmospheric oxidation of isoprene at low/moderate NOx. As a first photolysis mechanism, we show that a fraction of the initially excited S1-state HPALDs isomerizes by a near-barrierless 1,5 H-shift at a rate approaching 1012 s-1 - competing with the ∼equally fast intersystem crossing to the T2 triplet state - forming an unstable biradical that spontaneously expels an OH (hydroxyl) radical. A second mechanism is shown to proceed through the activated T2 triplet biradical - formed from S1 - undergoing a concerted ring-closure and OH-expulsion, yielding an oxiranyl-type co-product radical that quickly ring-opens to enoxy radicals. In both mechanisms, subsequent chemistry of the co-product radicals yields additional first-generation OH. The combined HPALD-photolysis quantum yield by these two mechanisms - which may not be the only photolysis routes - is estimated at 0.55 and the quantum yield of OH generation at 0.9, in fair accordance with experimental data on an HPALD proxy (Wolfe et al., Phys. Chem. Chem. Phys., 2012, 14, 7276-7286).

Surface Hydroxyl OH Defects of η-Al2O3 and χ-Al2O3 by Solid State NMR, XRD, and DFT Calculations

Abstract For the first time, the detailed structure of χ-Al2O3 and η-Al2O3 surface has been established by implementing the NMR crystallography approach. The surface of η-Al2O3 has been demonstrated to be formed primarily by the (111) facets, while the χ-Al2O3 surface is a combination of (111) and (110) facets. This observation supports the block model of aluminum oxides previously proposed by Tsybulya and Kryukova [S. V. Tsybulya, G. N. Kryukova, Phys. Rev. B 77 (2008) 024112.]. The additional terminal OH groups, observed experimentally and not contributing to (111) and (110) theoretical calculations, are considered to be bonded to the tetrahedral aluminum sites. Their origin is related to the junctions of crystallographic faces of spinel building blocks, being a part of discussed model. Higher content of these terminal OH groups in χ-Al2O3 is a result of more junctions in the case of its more mosaic structure compared to η-Al2O3.

Effect of Fe(II/III) on tetracycline degradation under UV/VUV irradiation

Abstract Photodegradation of tetracycline (TTC) under VUV/UV (185/254 nm) or sole UV (254 nm) irradiation in the presence of Fe(II/III) species was investigated at near-neutral pH (6.0–7.5) in pure water matrix. The VUV/UV process was more efficient to degrade TTC than sole UV process and the photodegradation rate was an order of magnitude higher. A relatively higher pH favored TTC photodegradation under both UV and VUV/UV irradiations. The effects of Fe(II/III) on TTC degradation under VUV/UV or sole UV irradiation were controlled by different reaction mechanisms. Fe(III) could promote TTC degradation under sole UV irradiation by complexation and subsequent oxidation, where the TTC degradation rate reached the maximum value ((14.7 ± 0.4) × 10 −3 min −1 ) at a Fe(III):TTC molar ratio of 1:1. The promotion of TTC degradation by Fe(III) under VUV/UV light can be negligible because of the dominated role of OH radicals produced by VUV/UV irradiation in TTC degradation. In contrast, Fe(II) facilitated TTC degradation under VUV/UV irradiation due to the additional OH radicals formed by the potential Fenton process. However, there was no obvious enhancement of TTC degradation with the addition of Fe(II) under sole UV irradiation. The total organic carbon (TOC) evaluation indicated Fe(II) and Fe(III) could enhance TTC mineralization under VUV/UV or sole UV irradiation. The electrical energy per order (EE/O) was also assessed and results suggested that VUV/UV (+Fe(II)) was a cost-effective way to degrade and mineralize TTC.

Phase state of ambient aerosol linked with water uptake and chemical aging in the southeastern US

Abstract. During the summer 2013 Southern Aerosol and Oxidant Study (SOAS) field campaign in a rural site in the southeastern United States, the effect of hygroscopicity and composition on the phase state of atmospheric aerosol particles dominated by the organic fraction was studied. The analysis is based on hygroscopicity measurements by a Hygroscopic Tandem Differential Mobility Analyzer (HTDMA), physical phase state investigations by an Aerosol Bounce Instrument (ABI) and composition measurements using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). To study the effect of atmospheric aging on these properties, an OH-radical oxidation flow reactor (OFR) was used to simulate longer atmospheric aging times of up to 3 weeks. Hygroscopicity and bounce behavior of the particles had a clear relationship showing higher bounce at elevated relative humidity (RH) values for less hygroscopic particles, which agrees well with earlier laboratory studies. Additional OH oxidation of the aerosol particles in the OFR increased the O : C and the hygroscopicity resulting in liquefying of the particles at lower RH values. At the highest OH exposures, the inorganic fraction starts to dominate the bounce process due to production of inorganics and concurrent loss of organics in the OFR. Our results indicate that at typical ambient RH and temperature, organic-dominated particles stay mostly liquid in the atmospheric conditions in the southeastern US, but they often turn semisolid when dried below ∼ 50 % RH in the sampling inlets. While the liquid phase state suggests solution behavior and equilibrium partitioning for the SOA particles in ambient air, the possible phase change in the drying process highlights the importance of thoroughly considered sampling techniques of SOA particles.

Production of pyrite nanoparticles using high energy planetary ball milling for sonocatalytic degradation of sulfasalazine

Sonocatalytic performance of pyrite nanoparticles was evaluated by the degradation of sulfasalazine (SSZ). Pyrite nanoparticles were produced via a high energy mechanical ball milling (MBM) in different processing time from 2h to 6h, in the constant milling speed of 320rpm. X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray (EDX), Fourier transform infrared spectroscopy (FT-IR) analysis and Brunauer–Emmett–Teller (BET) confirmed the production of pyrite nanoparticles during 6h of ball milling with the average size distribution of 20–80nm. The effects of various operational parameters including pH value, catalyst amount (mg/L), SSZ concentration (mg/L), ultrasonic frequency (kHz) and reaction time on the SSZ removal efficiency were examined. The obtained results showed that the maximum removal efficiency of 97.00% was obtained at pH value of 4, catalyst dosage of 0.5g/L, SSZ concentration of 10mg/L and reaction time of 30min. Experimental results demonstrated that the kinetic of the degradation process can be demonstrated using Langmuir–Hinshelwood (L-H) kinetic model. The effect of different inorganic ions such as Cl−, CO32− and SO42− was investigated on the L-H reaction rate (kr) and adsorption (Ks) constants. Results showed that the presence of the mentioned ions significantly influenced the L-H constants. The impact of ethanol as a OH radical scavenger and some enhancers including H2O2 and K2S2O8 was investigated on the SSZ removal efficiency. Accordingly, the presence of ethanol suppressed SSZ degradation due to the quenching of OH radicals and the addition of K2S2O8 and H2O2 increased the SSZ removal efficiency, due to the formation of SO4− and additional OH radicals, respectively. Under the identical conditions of operating parameters, pyrite nanoparticles maintained their catalytic activity during four consecutive runs.

The structures of interstitial hydrogen centers in VO2 in the dilute limit from their vibrational properties and theory

The introduction of a large concentration of H into VO2 is known to suppress the insulating phase of the metal–insulator transition that occurs upon cooling below 340 K. We have used infrared spectroscopy and complementary theory to study the properties of interstitial H and D in VO2 in the dilute limit to determine the vibrational frequencies, thermal stabilities, and equilibrium positions of isolated interstitial H and D centers. The vibrational lines of several OH and OD centers were observed to have thermal stabilities similar to that of the hydrogen that suppresses the insulating phase. Theory associates two of the four possible OH configurations for Hi in the insulating VO2 monoclinic phase with OH lines seen by experiment. Furthermore, theory predicts the energies and vibrational frequencies for configurations with Hi trapped near a substitutional impurity and suggests such defects as candidates for additional OH centers that have been observed.

Investigation of potential interferences in the detection of atmospheric RO<sub><i>x</i></sub> radicals by laser-induced fluorescence under dark conditions

Abstract. Direct detection of highly reactive, atmospheric hydroxyl radicals (OH) is widely accomplished by laser-induced fluorescence (LIF) instruments. The technique is also suitable for the indirect measurement of HO2 and RO2 peroxy radicals by chemical conversion to OH. It requires sampling of ambient air into a low-pressure cell, where OH fluorescence is detected after excitation by 308 nm laser radiation. Although the residence time of air inside the fluorescence cell is typically only on the order of milliseconds, there is potential that additional OH is internally produced, which would artificially increase the measured OH concentration. Here, we present experimental studies investigating potential interferences in the detection of OH and peroxy radicals for the LIF instruments of Forschungszentrum Jülich for nighttime conditions. For laboratory experiments, the inlet of the instrument was over flowed by excess synthetic air containing one or more reactants. In order to distinguish between OH produced by reactions upstream of the inlet and artificial signals produced inside the instrument, a chemical titration for OH was applied. Additional experiments were performed in the simulation chamber SAPHIR where simultaneous measurements by an open-path differential optical absorption spectrometer (DOAS) served as reference for OH to quantify potential artifacts in the LIF instrument. Experiments included the investigation of potential interferences related to the nitrate radical (NO3, N2O5), related to the ozonolysis of alkenes (ethene, propene, 1-butene, 2,3-dimethyl-2-butene, α-pinene, limonene, isoprene), and the laser photolysis of acetone. Experiments studying the laser photolysis of acetone yield OH signals in the fluorescence cell, which are equivalent to 0.05 × 106 cm−3 OH for a mixing ratio of 5 ppbv acetone. Under most atmospheric conditions, this interference is negligible. No significant interferences were found for atmospheric concentrations of reactants during ozonolysis experiments. Only for propene, α-pinene, limonene, and isoprene at reactant concentrations, which are orders of magnitude higher than in the atmosphere, could artificial OH be detected. The value of the interference depends on the turnover rate of the ozonolysis reaction. For example, an apparent OH concentration of approximately 1 × 106 cm−3 is observed when 5.8 ppbv limonene reacts with 600 ppbv ozone. Experiments with the nitrate radical NO3 reveal a small interference signal in the OH, HO2, and RO2 detection. Dependencies on experimental parameters point to artificial OH formation by surface reactions at the chamber walls or in molecular clusters in the gas expansion. The signal scales with the presence of NO3 giving equivalent radical concentrations of 1.1 × 105 cm−3 OH, 1 × 107 cm−3 HO2, and 1.7 × 107 cm−3 RO2 per 10 pptv NO3.

Measurement of Temperature Dependence for Vapor Pressures of Seventeen OH-PBDEs and Eleven MeO-PBDEs by Gas Chromatographic Method.

Hydroxylated polybromodiphenyl ethers (OH-PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) are emerging organic pollutants. Supercooled liquid vapor pressures (p L) and enthalpies of vaporization (∆vap H) for seventeen OH-PBDEs and eleven MeO-PBDEs were determined by a gas chromatographic technique. p L at 298 K ranged from 0.0173 Pa for 2'-OH-BDE3 to 2.32 × 10(-7) Pa for 3'-OH-BDE154 and they are approximately one order of magnitude smaller than those determined for the counterpart polybrominated diphenyl ethers (PBDEs). ∆vap H was in the range of 76-121 kJ/mol. The temperature dependence of p L was measured by fitting the experimental data with the log(p L/Pa) = a/(T/K) + b equation, and this corresponds to a 50-265 times higher p L value at 0 versus 30°C. Using fundamental quantum chemical descriptors, two quantitative structure-property relationship models (Q cum > 0.935) were developed to estimate p L at any temperature for the additional OH- and MeO-PBDE congeners.

Distribution of flavonoids among Malvaceae family members - A review

Since ancient times, Malvaceae family plant members are distributed worldwide and have been used as a folk remedy for the treatment of skin diseases, as an antifertility agent, antiseptic, and carminative. Some compounds isolated from Malvaceae members such as flavonoids, phenolic acids, and polysaccharides are considered responsible for these activities. Although the flavonoid profiles of several Malvaceae family members are investigated, the information is scattered. To understand the chemical variability and chemotaxonomic relationship among Malvaceae family members summation of their phytochemical nature is essential. Hence, this review aims to summarize the distribution of flavonoids in species of genera namely Abelmoschus, Abroma, Abutilon, Bombax, Duboscia, Gossypium, Hibiscus, Helicteres, Herissantia, Kitaibelia, Lavatera, Malva, Pavonia, Sida, Theobroma, and Thespesia, Urena, In general, flavonols are represented by glycosides of quercetin, kaempferol, myricetin, herbacetin, gossypetin, and hibiscetin. However, flavonols and flavones with additional OH groups at the C-8 A ring and/or the C-5′ B ring positions are characteristic of this family, demonstrating chemotaxonomic significance

Conditions and mechanisms for the formation of nano-sized Delafossite (CuFeO2) at temperatures ≤90 °C in aqueous solution

In this study, we present the mechanism of CuFeO2 formation in aqueous solution at low temperatures ≤90°C, using sulfate salts as reactants. Furthermore, we demonstrate the influence of experimental conditions (alkalization, reaction and ageing temperature and time) on the synthesized nanoparticles. In all cases, GR–SO4, a Fe(II–III) layered double hydroxysulphate (Fe2+4Fe3+2(OH)12·SO4) and Cu2O precipitate first. During further OH− supply GR–SO4 oxidizes and forms Fe10O14(OH)2, Cu2O and CuFeO2 crystals. Due to the high pH further CuFeO2 crystals grow at the cost of the unstable intermediate products. The reaction rate increases with increasing ageing temperature, reaction pH and, in particular, NaOH concentrations in the solution. As a result, highly crystalline CuFeO2 (3R and 2H polytypes) nanoparticles showing hexagonal morphology can be synthesized at 70°C within 10h or at 50°C within 1 week. The formation of 2H polytype is favored by additional OH− supply during the pH-stat time and rather low temperatures.

Sequential adsorption - photocatalytic oxidation process for wastewater treatment using a composite material TiO2/activated carbon

A composite material was tested to eliminate phenol in aqueous solution combining adsorption on activated carbon and photocatalysis with TiO2 in two different ways. A first implementation involved a sequential process with a loop reactor. The aim was to reuse this material as adsorbent several times with in situ photocatalytic regeneration. This process alternated a step of adsorption in the dark and a step of photocatalytic oxidation under UV irradiation with or without H2O2. Without H2O2, the composite material was poorly regenerated due to the accumulation of phenol and intermediates in the solution and on TiO2 particles. In presence of H2O2, the regeneration of the composite material was clearly enhanced. After five consecutive adsorption runs, the amount of eliminated phenol was twice the maximum adsorption capacity. The phenol degradation could be described by a pseudo first-order kinetic model where constants were much higher with H2O2 (about tenfold) due to additional OH radicals. The second implementation was in a continuous process as with a fixed bed reactor where adsorption and photocatalysis occurred simultaneously. The results were promising as a steady state was reached indicating stabilized behavior for both adsorption and photocatalysis.

Comparative sorption capacity of Pb(II) and Cd(II) by natural zeolite in phosphoric acid medium

Zeolite, a well-known inorganic compound, was used for Pb(II) and Cd(II) sorption. For this purpose, the model system composed with “H3PO4–Pb2+–Cd2+” medium was selected and applied with various amounts of both heavy metal salts. The results revealed that sorption capacity of the sorbent was higher for Pb2+ cation than in the diluted phosphoric acid (20% H3PO4) for all periods. The absorption of toxic metal ions was measured by atomic absorption spectroscopy. Different physical and chemical analysis techniques such as Fourier Transform infrared, scanning electron microscope, DTA, and XRD showed that natural state of zeolite in a diluted phosphoric acid (20% H3PO4) system underwent protonation and hydroxylation to produce additional OH− groups that are active in the sorption process and no destruction was observed in the structure.

Rapid oxidation and immobilization of arsenic by contact glow discharge plasma in acidic solution

Arsenic is a priority pollutant in aquatic ecosystem and therefore the remediation of arsenic-bearing wastewater is an important environmental issue. This study unprecedentedly reported simultaneous oxidation of As(III) and immobilization of arsenic can be achieved using contact glow discharge process (CGDP). CGDP with thinner anodic wire and higher energy input were beneficial for higher As(V) production efficiency. Adding Fe(II) in CGDP system significantly enhanced the oxidation rate of As(III) due to the generations of additional OH and Fe(IV) species, accompanied with which arsenic can be simultaneously immobilized in one process. Arsenic immobilization can be favorably obtained at solution pH in the range of 4.0–6.0 and Fe(II) concentration from 250 to 1000μM. The presence of organics (i.e., oxalic acid, ethanol and phenol) retarded the arsenic immobilization by scavenging OH or complexing Fe(III) in aqueous solution. On the basis of these results, a mechanism was proposed that the formed ionic As(V) rapidly coprecipitated with Fe(III) ions or was adsorbed on the ferric oxyhydroxides with the formation of amorphous ferric arsenate-bearing ferric oxyhydroxides. This CGDP-Fenton system was of great interest for engineered systems concerned with the remediation of arsenic containing wastewater.

Favreauite, a new selenite mineral from the El Dragón mine, Bolivia

Favreauite, ideally PbBiCu_6O_4(SeO_3)_4 • H_2O, is a new secondary selenite mineral from the El Dragon mine, Antonio Quijarro Province, Potosi Department, Bolivia. The mineral occurs in vughs in a matrix of (Co, Cu)-rich penroseite, dolomite and goethite. Associated minerals are: ahlfeldite, allophane, calcite, chalcomenite, malachite, molybdomenite and an unnamed Al selenite. Favreauite forms tiny green square tabular crystals, flattened on {001}, up to 0.1 mm on edge and 0.01 mm thick, occurring in subparallel and divergent groups. The Mohs hardness of favreauite is estimated as ≈3; it has perfect cleavage on {001}, an irregular fracture and a vitreous lustre. The calculated density based on the empirical formula is 4.851 g cm^(−3). Favreauite is uniaxial (−), with mean refractive index estimated as 1.854 from the Gladstone–Dale relationship. It is pleochroic in shades of green, O 4σF_o] and 0.0356 for all 1432 unique reflections. Favreauite is a close structural relative of nabokoite, KCu_7Te^(4+)O_4(SO_4)_5Cl, and atlasovite, KCu_6Fe^(3+)BiO_4(SO_4)_5Cl. In all cases, oxygen-centred tetrahedra share edges to form corrugated [Cu_6MO_4] layers (M = Bi or Te) which can be derived from the framework structure of murdochite, Pb^(4+)Cu^(2+)_6O_(8-x)(Cl,Br)_(2x) by selective deletion of atoms. In favreauite, additional OH and H_2O between the layers are weakly bound to Cu, giving it Jahn-Teller distorted 4 + 2 coordination. The Cu–Bi–O layer is braced by SeO_3 pyramids. The Bi^(3+) and interlayer Pb^(2+) form an approximately face-centred cubic array analogous to the Pb^(4+) sites in murdochite. Unlike Bi^(3+), Pb^(2+) is in a site with nonpolar Formula point symmetry, which suppresses the stereoactivity of its lone pair.