Effect of initial pH on chalcopyrite oxidation dissolution in the presence of extreme thermophile Acidianus manzaensis

The influence of initial pH on the chalcopyrite oxidation dissolution at 65 ℃ was investigated by bioleaching and cyclic voltammetiy experiments,and the oxidation products were investigated by XRD and Raman spectroscopy.Bioleaching results show that chalcopyrite dissolution rate increases with the decrease of the initial pH in chemical leaching,while the influence of initial pH on bioleaching is on the contrary.The presence of Acidianus manzaensis does not promote chalcopyrite dissolution under initial pH1.0,which mainly results from serious inhibition of high acidity to the growth of Acidianus manzaensis.Electrochemical experiments results show that anodic oxidation currents of electrolyte with or without Acidianus manzaensis both increase with the increase of initial pH,and covellite and sulfur are detected on the electrode surface.The results confirm that chalcopyrite dissolution in chemical leaching is under the combined action of oxidation and non-oxidation of proton,with conversion of chalcopyrite to covellite and elemental sulfur.

Crack Propagation in Pipelines Under Extreme Conditions of Near-Neutral PH SCC

Stress Corrosion Cracking(SCC)process through which cracks occur in a variety of susceptible materials is a result of a combination of residual or applied stresses and corrosion.In oil and gas field,buried pipeline steels are made of low-alloy steels with a ferritic-pearlitic structure,such as X70.In dilute solutions,these materials are prone to SCC failure.The Near-neutral simulated soil solution(NS4)solution is established to imitate SCC conditions and subsequently became the industry requirement for crack growth experiments in the majority of laboratories.The strainassisted active crack pathways are considered while modelling SCC growth as an oxide film rupture and anodic dissolution process.It’s been hypothesized that increasing the strain concentration can help with dissolution at the filmfree crack tip.This research focuses on estimating the SCC crack growth rate under various environmental conditions in oil and gas pipelines using finite element modelling.The simulation is carried out using the J-integral theory in the COMSOL Multiphysics program.Simulations are performed to model the crack growth rate(CGR)using slip anodic dissolution(film rupture)mechanism.The plastic strain gradient is required to compute the SCC CGR(da/dt).Because the plastic strain located at crack tip increases proportionally to the crack length as it propagates,the CGR increases as the stress intensity factor(SIF)increases.The crack growth rates increase when constant loads are applied and as the temperature rises,and elevating the cathodic potential has a minimal influence on the propagation rate of cracks but raises the material yield strength and imparts brittle behavior to it.

Induced transformation of antimony trioxide by Mn(II) oxidation and their co-transformed mechanism

Antimony(Sb)is a toxic and carcinogenic element that often enters soil in the form of antimony trioxide(Sb_(2)O_(3))and coexists with manganese(Mn)in weakly alkaline conditions.Mn oxides such as birnessite have been found to promote the oxidative dissolution of Sb_(2)O_(3),but few researches concerned the co-transformations of Sb_(2)O_(3) and Mn(II)in environment.This study investigated themutual effect of abiotic oxidation of Mn(II)and the coupled oxidative dissolution of Sb_(2)O_(3).The influencing factors,such as Mn(II)concentrations,pH and oxygen were also discussed.Furthermore,their co-transformed mechanism was also explored based on the analysis of Mn(II)oxidation products with or without Sb_(2)O_(3) using XRD,SEM and XPS.The results showed that the oxidative dissolution of Sb_(2)O_(3) was enhanced under higher pH and higher Mn(II)loadings.With a lower Mn(II)concentration such as 0.01 mmol/L Mn(II)at pH 9.0,the improved dissolution of Sb_(2)O_(3) was attributed to the generation of dissolved intermediate Mn(III)species with strong oxidation capacity.However,under higher Mn(II)concentrations,both amorphous Mn(III)oxides and intermediate Mn(III)species were responsible for promoting the oxidative dissolution of Sb_(2)O_(3).Most released Sb(∼72%)was immobilized by Mn oxides and Sb(V)was dominant in the adsorbed and dissolved total Sb.Meanwhile,the presence of Sb_(2)O_(3) not only inhibited the removal of Mn(II)by reducing Mn(III)to Mn(II)but also affected the final products of Mn oxides.For example,amorphous Mn oxides were formed instead of crystalline Mn(III)oxides,such as MnOOH.Furthermore,rhodochrosite(MnCO_(3))was formed with the high Mn(II)/Sb_(2)O_(3) ratio,but without being observed in the low Mn(II)/Sb_(2)O_(3) ratio.The results of study could help provide more understanding about the fate of Sb in the environment and the redox transformation of Mn.

Kinetics of FeSe_2 oxidation by ferric iron and its reactivity compared with FeS_2

The mobility and bioavailability of selenium is a major health and environmental issue and a main concern for geological disposal of high-level radioactive waste. Chemically and/or microbially mediated oxidation of insoluble Se-bearing particulate, such as iron selenides, to dissolved and mobile phases controls the transport and distribution of Se in the environment. The oxidation of ferroselite （FeSe2） by ferric iron was investigated in anoxic conditions. The redox reaction can be represented by： FeSe2 ＋ 2Fe3＋ = 2Se^0 ＋ 3Fe2＋. Kinetic studies indicated that the reaction can be described by second-order rate law, with rate constants of 0.49±0.01, 0.85±0.02, 1.84±0.04, and 3.29±0.13 L mol^-1 s^-1 at pH 1.62, 1.87, 2.23, and 2.49, respectively. The positive correlation between reaction rate and pH implies that diffusion of Fe3＋ oxidant to the mineral surface is the rate-determining step. The strong reactivity of FeSe2 towards Fe^3＋ suggests that ferric iron may play a significant role in FeSe2 oxidation process （e.g., by Se^4＋, 02, etc.） and Se^0 should be the first reaction product. Also, it was shown that the reduction rate of Fe^3＋ or Se^4＋ by pyrite （FeS2） can be significantly increased in the presence of FeSe2, suggesting a stronger reactivity of FeSe2 compared with pyrite. The results obtained extend our knowledge about the subtle interaction between Se, pyrite and iron selenides in the environment, and give insight into the transfer of selenium from iron selenides to bio-available selenium （i.e., selenite and selenate） in the Se-rich environment.

Substrate mediated dissolution of redox active nanoparticles;electron transfer over long distances

Reflective dark field microscopy is used to observe the decrease in the light scattered from Ag nanoparticles immobilised on differing solid substrates.The nanoparticles are exposed to solutions containing halide ions,both at open circuit and under potentiostatic control,leading to the loss of the nanomaterial.By coupling optical and electrochemical techniques the physical origin of this transformation is demonstrated to be the electrochemical dissolution of the metal nanoparticles driven by electron transfer to ultra-trace dissolved oxygen.The dissolution kinetics of the surface-supported metal nanoparticles is compared on four substrate materials(i.e.,glass,indium titanium oxide,glassy carbon and platinum)with different electrical conductivity.The three conductive substrates catalyse the redox-driven dissolution of Ag nanoparticles with the electrons transferred from the nanoparticles,via the macroscopic electrode to the dioxygen electron acceptor.

Cavitation erosion behavior of CLAM steel weld joint in liquid lead-bismuth eutectic alloy

The cavitation erosion of weld joint and base metal of China low activation martensitic（CLAM）steel in liquid lead-bismuth eutectic alloy（LBE）at 550°C was investigated to simulate the cavitation erosion of the first wall and the nuclear main pump impeller in the accelerator driven sub-critical system（ADS）.A suit of ultrasonic cavitation facility was self-designed to study the cavitation erosion.By studying the surface micro topography,roughness and mean pit depth of the tested specimens,it was found that some crater clusters and large scale cracks appeared on the tested specimen surface after the formation of numerous single craters,and the base metal exhibited much better cavitation erosion resistance than the weld bead due to the difference in their mechanical properties and microstructures.In addition,by comparing the results of static corrosion and cavitation erosion,it could be concluded that the cavitation erosion and the dissolution and oxidation corrosion in liquid LBE would accelerate mutually.