Artykuły w czasopismach na temat „NaCl solid deposit”

A comprehensive corrosion investigation of pure Fe in an environment of solid sodium salt deposit (i.e., NaCl or Na2SO4) with mixtures of H2O and O2 at 500°C was conducted by mass gain measurement, X-ray diffraction (XRD), scanning electron microscope (SEM), potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS). The results showed that corrosion rates were accelerated with solid NaCl or Na2SO4 deposit due to their reaction with the formed protective scale of Fe2O3 and subsequently resulted in its breakdown. The corrosion rate of pure Fe with solid NaCl is higher than that with solid Na2SO4 because of the lower activation energy (Ea) for chemical reaction of Fe in solid NaCl+H2O+O2 (i.e., 140.5 kJ/mol) than that in solid Na2SO4+H2O+O2 (i.e., 200.9 kJ/mol). Notably, the electrochemical corrosion rate of pure Fe with solid NaCl deposit, 1.16×10−4 A/cm2, was a little lower than that with solid Na2SO4 deposit.

Titanium alloys are widely used in aerospace applications due to their good ratio of weight versus mechanical properties. When exposed to air at 560°C, Ti6242S titanium alloy presents very good oxidation resistance: a very thin oxide layer forms at its surface and oxygen dissolution inside the metallic material is rather limited. However, in real functioning conditions of the plane, near seas or oceans, the atmosphere contains NaCl, that can crystallise at the surface of hot parts. An active corrosion mechanism is established in these conditions, with catastrophic effect on the material behaviour at high temperature: very thick and brittle oxide scales and very important damaging of the metal outer part. Another issue is the formation of Na2SO4 specie by reaction of NaCl with kerosene combustion gases (SO2/SO3), leading to mixed NaCl/Na2SO4 deposits. The effect of exposure conditions on the mechanical properties of titanium alloy Ti6242S was evaluated through tensile tests performed on the raw alloy and after oxidation in air at 560°C of the specimens: without any deposit, with NaCl solid deposit, with NaCl/Na2SO4 solid deposit. The evolution of mechanical properties was interpreted in connexion with the microstructural modifications that occur during the high temperature ageing.

The Wushan copper polymetallic deposit is located in the Tongbai-Dabie orogenic belt in central China. Two small granitoid stocks (Donggushan and Xigushan) occur in the deposit, which is next to the largest Qijianfeng Granite Complex in the Suizao area. The mineralization of Wushan copper polymetallic deposit is mainly composed of ore-bearing quartz veins and quartz stockworks. Two hydrothermal stages are identified as the quartz-sulfide stage (early stage) and the barren quartz stage (late stage). A detailed petrographic study shows four types of fluid inclusions in quartz, including the aqueous fluid inclusions (L+V/V+L), the aqueous-carbonic fluid inclusions (L+V+CO2), the pure carbon dioxide fluid inclusions (pure CO2), and the daughter mineral-bearing multiphase fluid inclusions (S). The daughter mineral-bearing multiphase fluid inclusions (S) are further divided into three subclasses according to their different solid mineral assemblages, including (1) S1: L+V+Hal, (2) S2: L+V+CO2+S (chalcopyrite), and (3) S3: L+V+S (calcite, chalcopyrite, and hematite)±Hal. A laser Raman spectroscopic analysis shows that the main components of fluid inclusions are water and carbon dioxide. The solid minerals of the S-type fluid inclusions include halite, calcite, chalcopyrite, and hematite. The homogenization temperatures of fluid inclusions are 377 to 468°C for the early stage, with a salinity of 11.1 to 34.1 wt.% NaCl equivalent (11.1 to 17.4 wt.% NaCl equivalent and 28.4 to 34.1 wt.% NaCl equivalent, respectively) and an estimated pressure of 89 to 137 MPa. The homogenization temperatures of fluid inclusions in the late stage are 267 to 380°C with salinity of 7.0 to 12.1 wt.% NaCl equivalent and an estimated pressure of 46 to 115 MPa. Therefore, the temperature, salinity, and pressure of the fluid show a decreasing trend from the early to the late stage. In the early stage, the fluid is immiscible, which leads to the precipitation of sulfides. Pyrite shows a δ34S of approximately 0 (-1.8 to +3.4‰), and chalcopyrite also shows a similar δ34S of approximately 0 (+1.5 to +2.4‰), which indicates that the sulfur in the ore-forming fluid is mainly derived from deep-seated magma. Combined with C-H-O isotopic compositions, the initial ore-forming fluid is likely magmatic water, but with the addition of meteoric water in the late stage. By comparing with the typical characteristics of magmatic hydrothermal vein deposit and orogenic deposit related to shear zones, we suggest that the Wushan copper polymetallic deposit is most likely a magmatic hydrothermal vein deposit, which is of great significance for the further exploration work in the Wushan and surrounding areas. This new finding also fills the gap that no magmatic hydrothermal vein type Cu deposits have been found in the Suizao area or even in the Qinling-Dabie orogenic belt in central China.

The mineral and chemical compositions of ores from the Corrida epithermal Au-Ag deposit (Chukchi Peninsula, Russia) were studied using the optical and scanning electron microscopy with X-ray energy-dispersion microanalysis. The deposit was formed at the time close to the period when the basic volume of acid magmas had been emplaced within the Okhotsk–Chukotka belt (84 to 80 Ma). The Au–Ag mineralization is distinguished with Au-Ag sulphides and selenides (uytenbogaardtite-fischesserite solid solution, Se-acanthite, S-naumannite) and Ag halides of the chlorargyrite-embolite-bromargyrite series. The ores were formed in two stages. Using microthermometric methods, it has been established that the ore-bearing quartz was formed in the medium-temperature environment (340–160 °C) with the participation of low-salt (3.55 to 0.18 wt.% NaCl eq.) hydrotherms, mostly of the NaCl composition with magnesium, iron and low-density СО2. According to our results of thermodynamic modeling at temperatures from 300 to 25 °C and data on mineral metasomatic alterations of the host rocks, the Au-Ag-S-Se-Cl-Br mineralization was formed at decreasing temperature and fugacity of sulphur (logƒS2 from −6 to −27), selenium (logƒSe2 from −14 to −35), and oxygen (logƒО2 from −36 to −62), with near-neutral solutions replaced by acid solutions. Analysis of the obtained data shows that the Corrida refers to the group of the LS-type epithermal deposits. This deposit is a new example of epithermal deposits with significant quantities of Au–Ag chalcogenides (acanthite, uytenbogaardtite, fischesserite, naumannite and others).

The hot corrosion behavior of titanium alloy and AlCuFeCr quasicrystalline coating on titanium alloy in the presence of a solid mixture of NaCl and Na2SO4 deposit at 700°C was studied. The result shows that weight-gain kinetics for titanium alloy exhibited a linear rate law, while the kinetics of AlCuFeCr quasicrystalline coating displayed parabolic growth rate. The corrosion resistance of the titanium alloy was improved by applying the AlCuFeCr quasicrystalline coating. The corrosive oxide morphology formed on titanium alloy was porous. For AlCuFeCr quasicrystalline coating with the mixture of NaCl and Na2SO4 deposit, the scale formed on the coating surface was compact and uniform. Oxide formed on the surfaces of Al-Cu-Fe-Cr quasicrystalline coatings after hot corrosion consisted of Al2O3.

There are many celestine deposits and mineralization points in the Huayingshan ore district which form the largest strontium resource base in China. Among these celestine deposits, the Yuxia and Xinglong are two of the larger deposits. Previous studies have displayed different views on the genesis of the celestine deposit in the Huayingshan ore district. In this study, we conducted field obversions, geochemistry, and fluid inclusion studies to investigate the sources of ore-forming matters and the metallogenic mechanism of the celestine deposit. Four types of fluid inclusion (FI), namely PL (pure liquid FI), PV (pure vapor FI), L-V (liquid-vapor two-phase FI), and L-V-S (liquid-vapor-solid three-phase FI) have been identified in celestine from different types of ore in the Xishan anticline. The ore-forming fluids belong to the NaCl-H2 O system with moderate to low temperature (190–220 °C) and moderate salinity (5–9 wt%, NaCl equiv.). Different types of ores were formed by the same period of hydrothermal activity, which is supported by the results of the microthermometer study. Geological, thermometric data, and published hydrogen and oxygen isotope results indicate that the hot brines associated with mineralization mainly originated from meteoric water and some of diagenetic fluid. The Sr (87Sr/86Sr = 0.7076–0.7078) and S (δ34S = 36.4–39.0) isotope values of celestine are consistent with those of the Jialingjiang Formation, indicating that ore metals in hot brines were predominantly derived from that formation. In situ analysis of celestine shows that there is a strong negative correlation between Sr and CaO (R2 = 0.95) and combined with mineralogical and isotope geochemical evidence, we concluded that the precipitation mechanism of celestine is the replacement of gypsum with Sr-rich hot brines. Based on the above research and the classification of celestine deposit type, we classified the celestine deposits in Huayingshan as being of hydrothermal type. The formation of celestine deposits can be divided into three periods: (1) evaporation period, forming the source bed; (2) hydrothermal activity period, forming celestine by replacement of gypsum with Sr-rich hot brines; (3) supergene period, where meteoric water dissolves orebodies and strontianization occurs.

Uranium can be found in the Earth’s crust in different reservoirs, with igneous rocks being the primary source of this element from which many types of secondary deposits are formed. Fluorspar deposits generally do not contain uranium, but in some cases, fluorite can carry both uranium in solid solutions and inclusions of uranium minerals. We studied the concentration (ICP-MS), composition (electronic microprobe), and spatial distribution (microscopy and auto-radiography) of elemental uranium and uranium minerals at different scales (microscopy and auto-radiography in fluorite from the La Azul fluorspar deposit (Taxco, Mexico) to assess the origin of uranium and its significance in this ore deposit. Auto-radiography images with the CR-39 detector were found to be impressive in their ability to elucidate uranium distribution at the millimeter scale. The limit between the solid solution of elemental uranium in natural fluorite and the appearance of uranium oxides as inclusions appeared to be between 20 μg g−1 and 40 μg g−1 bulk uranium concentration in this fluorspar ore. The maximum concentration of U in fluorite from the La Azul deposit was about 100 μg g−1. Using Raman spectroscopy and microprobe analysis, we identified the micro-inclusions of uranium minerals as uraninite (of the pitchblende variety); its composition suggested a hydrothermal origin for this fluorspar deposit. We also calculated a chemical age that can be compared with the previously published regional geology and isotopic (U-Th-Sm)/He ages in fluorite. Micro-thermometric studies of fluid inclusions were carried out in different samples of uranium-rich fluorite to identify the nature and origin of the mineralizing fluid and the precipitation mechanisms of uranium minerals. We concluded that the uranium-rich fluorite precipitated in the initial phases of mineralization from a reducing fluid, with low salinity (<8% NaCl eq.) and an intermediate temperature (110–230 °C), and that the presence of organic compounds and sulfides (mainly pyrite) favored the simultaneous precipitation of uraninite (pitchblende variety) and fluorite.

AbstractThe compositions of fluid inclusions hosted in emerald and quartz (the Maria deposit, Mozambique) were studied using microthermometric and Raman microprobe techniques. The fluid inclusions in the emerald contain fluids within the Na-Ca-Mg-(HCO3)−-(CO3)2−-Cl-H2O system saturated in carbonic acid brines. Nahcolite is a main daughter solid phase within the fluid inclusions. The mean nahcolite and NaCl contents are 25 and 5 wt.%, respectively. Mg-calcite, magnesite, calcite and aragonite are also identified as daughter phases in the fluid inclusions. Many fluid inclusions show necked-down appearance. Groups of nahcolite crystals often make up ∼50 vol.% of necked-down inclusions. It seems that zones of fluid inclusions with numerous birefringent solid phases are distinctive of the Maria emerald deposit. The likely conditions of emerald growth are 400 < T < 500°C and 3 < P < 4 kbar.

Microscopic examination was used to begin investigating the changes in geosynthetic clay liner (GCL) specimens that had been hydrated with two separate solutions: pure water and a 50 percent concentration NaCl solution. After already being hydrated with NaCl aqueous solution, the GCL samples were examined under an electron microscope. Even though the treated GCL samples’ surfaces mirrored those of the untreated GCL, a crystal deposit was found there. It was found that the bentonite particles in the GCL sample appeared more solid after being hydrated with distilled water as opposed to the NaCl solution using a scanning electron microscope (SEM). It seems that wetting the salt solution decreases the bentonite particles’ tendency to swell. Additionally, it was demonstrated by the energy-dispersive X-ray spectrometer (EDS) data that distilled water hydration had no impact on the distribution of the elements identified in the GCL samples. On the other hand, the presence of bound chlorine demonstrated that the bentonite particles had absorbed the NaCl solution. The hydrated GCL sample’s hydraulic conductivity showed some variation as well.

Morphological variations of geosynthetic clay liner (GCL) samples, hydrated with two different permeates, distilled water and NaCl solution (100 mM concentration), were observed in detail using microscopic analysis. After the GCL samples were hydrated with the NaCl solution, they were observed with an optical microscope. While the surface of the treated GCL samples was similar to the surface of the untreated GCL, a crystal deposit was found on the surface of the treated samples. Using a scanning electron microscope (SEM), a more solid appearance was observed for the bentonite particles contained in the GCL after the sample was hydrated with distilled water in comparison to the GCL sample that was hydrated with the NaCl solution. It appears that salt solution hydration results in less swelling of the bentonite particles. Furthermore, the energy-dispersive X-ray spectrometer (EDS) results showed that distilled water hydration had no effect on the distribution of the elements contained in the GCL samples. However, bound chlorine was observed, which demonstrated that the bentonite particles had absorbed the NaCl solution. In addition, changes in the hydraulic conductivity of the hydrated GCL samples were also observed.

This article presents a new method for preparing a coating on Ti65 titanium alloy using a two-step procedure comprising hot-dipped aluminum and solid carburization. The effects of the carburization on the hot-dipped aluminum coating against the presence of a NaCl deposit at 810 °C were systematically studied. In this article, the microstructure, morphology, phase composition of the coating, and corrosion products were investigated using SEM (Scanning Electron Microscopy), EDS (Energy Dispersive Spectrometer), and X-ray diffraction. The results indicated that the corrosion resistance of the hot-dip aluminum/carburizing composite coating was not significantly enhanced with the hot-dip aluminum coating. This can be attributed to the formation of TiC and Ti3AlC after carburization, which promoted the formation of loose and unprotected TiO2 in the coating during molten salt corrosion. In addition, the oxidation of the carbon atom into CO2 led to a high concentration of pores in the coating, creating channels for NaCl to penetrate the coating and accelerate the corrosion rate.

Abstract Hydrothermal alteration of the Meiduk porphyry copper deposit, south of the Kerman Cenozoic magmatic arc and southeast of the central Iranian volcano-plutonic belt has resulted in three stages of mineralisation characterised by veins and veinlets. These are, from early to late: (1) quartz + K-feldspar + biotite + pyrite ± chalcopyrite ± pyrrhotite ± magnetite (early potassic alteration and type-A veins); (2) quartz + chalcopyrite + pyrite + bornite + pyrrhotite + K- -feldspar + biotite + magnetite (potassic-sericitic alteration and type-B veins); and (3) quartz + pyrite + chalcopyrite + sericite (sericitic alteration and type-C veins). Most ores were formed during stages 2 and 3. Three main types of fluid inclusions are distinguished based on petrographical, microthermometrical and laser Raman spectroscopy analyses, i.e. type I (three-phase aqueous inclusions), type II (three-phase liquid-carbonic inclusions) and type III (multi-phase solid inclusions). The fluid inclusions in quartz veins of the stages are mainly homogenised at 340-530°C (stage 1), 270-385°C (stage 2) and 214-350°C (stage 3), respectively, with salinities of 3.1-16 wt.% NaCl equivalent, 2.2-43 wt.% NaCl equivalent and 8.2-22.8 wt.% NaCl equivalent, respectively. The estimated trapping pressures are 97.9-123.6 MPa (3.7-4.6 km) in stage 1 and 62.5-86.1 MPa (2.3-3.1 km) in stage 2, respectively. These fluid inclusions are homogenised in different ways at similar temperatures, suggesting that fluid boiling took place in stages 2 and 3. The fluid system evolved from high-temperature, medium-salinity, high-pressure and CO2-rich to low-temperature, low-pressure, high-salinity and CO2-poor, with fluid boiling being the dominating mechanism, followed by input of meteoric water. CO2 escape may have been a factor in increasing activities of NaCl and S2- in the fluids, diminishing the oxidation of the fluids from stage 1 to 3. The result was precipitation of sulphides and trapping of multi-phase solid inclusions in hydrothermal quartz veins.

The Nanmingshui gold deposit, located in the eastern segment of the Kalamaili gold belt (KGB), is hosted by the sub-greenschist facies rocks of the Lower Carboniferous Jiangbasitao Formation. The genesis of this deposit, however, has been debated for decades because of controversial constraints on the P-T-X conditions and origins of hydrothermal fluid and mineralization age. In this study, we present gold-bearing sulfide compositions, fluid inclusions, H-O isotopes, and the results of hydrothermal zircon U-Pb dating to provide new insights into the genesis of the gold deposit. Three gold mineralization stages are recognized: quartz–pyrite–minor native gold veins (early), quartz–tourmaline–arsenopyrite–pyrite–gold–polymetallic sulfide veins (middle), and quartz–calcite veinlets (late). Gold predominantly occurs as native gold with high fineness ranging from 941 to 944 in sulfides and quartz, and some as solid solutions (Au+) within the lattice of pyrite and arsenopyrite. Three types of primary fluid inclusions are identified in hydrothermal quartz: CO2-H2O (C-type), aqueous (W-type), and pure CO2 (PC-type) inclusions. The early-stage quartz mainly contains C-type and minor W-type inclusions, with total homogenization temperatures (Th) of 220–339 °C, salinities of 0.4–3.7 wt.% NaCl eqv., and bulk densities of 0.66–1.01 g/cm3. All three types of inclusions are observed in the middle-stage quartz, of which the C- and W-type inclusions yield Th values of 190–361 °C, with salinities of 0.4–6.0 wt.% NaCl eqv. and bulk densities of 0.69–0.99 g/cm3. The late-stage quartz contains only W-type inclusions that have lower Th values of 172–287 °C, higher salinities of 1.4–6.9 wt.% NaCl eqv., and bulk densities of 0.79–0.95 g/cm3. Trapping pressures estimated from C-type inclusions in the early and middle stages cluster at 280–340 MPa and 220–310 MPa, respectively, corresponding to metallogenic depths of 10–13 km and 8–11 km. The H-O isotopic compositions (δ18Owater = 1.8–10.9‰, δD = −99 to −62.9‰) and microthermometric data indicate that the ore-forming fluids belong to medium–high-temperature, low-salinity, medium-density, and CO2-rich-H2O-NaCl ± CH4 ± N2 systems, probably originating from metamorphic water. Fluid immiscibility is a crucial mechanism for gold precipitation. Additionally, the U-Pb dating of hydrothermal zircons, from the auriferous quartz–tourmaline vein, yield a weighted mean 206Pb/238U age of 314.6 ± 9.6 Ma. Taking all of the above, the Nanmingshui deposit can be reasonably classed as a typical mesozonal orogenic gold deposit in the KGB, which was formed in a Late Carboniferous tectonic transition from syn-collision between the Jiangjunmiao accretionary complex and Yemaquan arc to post-collision in the East Junggar Orogen. Our results serve to better understand the gold mineralization and genesis of the Late Paleozoic orogenic system in the Kalamaili area, Xinjiang.

Research subject. Au-Pd mineralization of the Bleïda Far West deposit, represented by an unusual association of palladium gold, minerals of the Pd-Bi-Se system, as well as silvery gold and minerals of the Pd-Bi-Te system. The deposit is localized in the Neoproterozoic volcanic rocks of the central Anti-Atlas (Morocco).Methods. A chemical analysis of minerals was carried out at the Center for Collective Use of Multielement and Isotopic Studies of the Siberian Branch of the Russian Academy of Sciences (Novosibirsk, Russia) using the electron probe microanalysis (EPMA) method. Fluid inclusions were studied using cryometry and homogenization using a THMSG-600 microthermochamber. The composition of the gas phase and the determination of the solid phases of the inclusions were carried out by Raman spectroscopy. The qualitative chemical composition of fluid inclusion salts was determined by the EPMA method.Results and conclusions. It is suggested that palladium gold and minerals of the Pd-Bi-Se system were formed under the conditions close to those during the formation of Au-Pd infiltration deposits in Brazil, while silvery gold and minerals of the Pd-Bi-Te system could be formed under the conditions similar, but not identical, to the formation conditions of Au-Pd low-temperature mineralization in porphyry deposits. According to the study of fluid inclusions in quartz and calcite, Au-Pd mineralization was formed at temperatures from 384 to 75°C with the participation of homogeneous or heterophasic CaCl2-NaCl highly saline hydrothermal solutions at a depth of 2.8–2.7 km. Minerals of the Pd-Bi-Se system, previously unknown in Bleïda Far West ores, were found in association with native gold: osterboshite (Pd, Cu)7Se5, paladsite (Pd17Se15), (Au,Ag)Se, padmaite PdBiSe, native Se, as well as a number of unidentified phases – Pd2BiSe, Pd3BiSe, Pd4BiSe and Pd5BiSe.

The Baranyevskoe Au-Ag epithermal deposit of low-sulfidation (LS) type is located on the Kamchatka Peninsula in the Neogene-Quaternary Central Kamchatka Volcanic Belt, where Au-bearing quartz veins are usually accompanied by veinlet stockworks. Two economic associations are typical of the Baranyevskoe deposit. The first corresponds to gold-pyrite-quartz association with low-grade native gold (521–738‱) intergrown with pyrite. Some accessory Au-Ag minerals within the early association were also identified: acanthite AgS2, hessite AgTe2, lenaite Ag(Fe,Cu)S2, petzite Ag3AuTe2, utenbogardite Ag3AuS2 and unnamed Ag-Sb-As sulfosalts. The former Au-Ag minerals were most likely formed in the temperature range of 320–330 °C based on the study of arsenopyrite thermometers and fluid inclusions. The second, a gold-sulfosalt-quartz association, includes high-grade native gold (883-941‱) in intergrowth with chalcopyrite. Cuprous phases (bornite, chalcocite, heerite, native copper, Cu-Zn solid solutions), Bi-rich sulfosalts (aikinite PbCuBiS3, emplectite CuBiS2, witticenite Cu3BiS3), stannoidite Cu8Fe3Sn2S12, mawsonite Cu6Fe2SnS8), Au-bearing galena, Te-free and Bi-rich tetrahedrite-tennantite represent this association. Fluid inclusions in gold-sulfosalt-quartz association are characterized by homogenization temperature ranging from 226 to 298 °C, and salinity from 0.4 to 1.2 wt. % NaCl eq.

The Bayan-Uul porphyry Au-Cu-(Mo) deposit occurs within the Mongol–Okhotsk Orogenic Belt, which is a part of the Central Asian Orogenic Belt. To understand geotectonic, petrogenesis, mineralization, and ore-forming fluid evolution of the Bayan-Uul deposit, we report petrographic and geochemical analyses of host rocks, mineralogy of ores, and fluid inclusion characteristics. Based on petrographic and mineralogical analyses, Cu, Mo, and Au mineralization occurs as disseminated and sulfide-bearing quartz–tourmaline veins hosted within granodiorites, monzodiorites, and diorite porphyry and tourmaline breccia. Four main alteration assemblages are identified: potassic, phyllic, argillic, and quartz–tourmaline alteration. The ore mineralogy of quartz–tourmaline veinlets are classified into A-type veinlets (quartz + tourmaline + chalcopyrite + magnetite + pyrite ± electrum), B-type veinlets (quartz + tourmaline + molybdenum + chalcopyrite + pyrite), and C-type veinlets (quartz + tourmaline + pyrite ± chalcopyrite). Fluid inclusions are found in quartz–tourmaline veinlets consisting mainly of liquid-rich two-phase (L-type), vapor-rich two-phase (V-type), and solid-bearing multi-phase (S-type) inclusions. The homogenization temperatures for the fluid inclusions in A-type, B-type, and C-type veinlets range from 215 to 490°C, 215 to 500 °C, and 160 to 350 °C and their salinity varies from 5.4 to 43.5 wt.%, 16 to 51.1 wt.%, and 3.4 to 24.1 wt.% NaCl equivalent, respectively. Coexistance of (L-type), (V-type), and (S-type) inclusions support fluid boiling. The δ18O values of ore fluids from different mineralizing A-, B-, and C-type veins are 8.7‰, 10.9‰, and 8.4‰, respectively, and the δ34S values of sulfide minerals range from −1.4‰ to 5.3‰, which indicates magmatic origin.

ABSTRACTAround the radioactive waste repository, the pH of the groundwater greatly changes from 8 to 13 and the groundwater contains a relatively large quantity of calcium (Ca) and sodium (Na) ions due to cementitious materials used for the construction of the geological disposal system. Under such conditions, the deposition behavior of silicic acid is one of the key factors for the migration assessment of radionuclides. The deposition and precipitation of silicic acid with the change of pH and coexisting ions may contribute to the clogging in flow paths, which is expected as the retardation effect of radionuclides. Thus, this study focused on the deposition behavior of silicic acid under the condition of relatively high Ca or Na concentration.In the experiments, Na2SiO3 solution (250 ml, 14 mM, pH>10, 298 K) was prepared in a polyethylene vessel containing amorphous silica powder (0.5 g) as the solid phase. Then, a buffer solution (to adjust to 8 in pH), HNO3, and Ca(NO3)2 as Ca ions or NaCl as Na ions were sequentially added. Such a silicic acid solution becomes supersaturated, gradually forming colloidal silicic-acid and/or the deposit on the solid surface. In this study, the both concentrations of soluble and colloidal silicic-acid were monitored over a 40-day period. As a result, the deposition rate of silicic acid decreased with up to 5 mM in Ca ions. Besides, Na ions with up to 0.1 M slightly increased the deposition rate. Under the conditions of [Na+]>0.1 M or [Ca2+]>5 mM, the supersaturated silicic acid immediately deposited. These suggest that Na or Ca ions strongly affect the deposition behavior of supersaturated silicic-acid, depending on the surface alteration of solid phase, the change of zeta potential and the decrease of water-activity due to the addition of electrolytes (coexisting ions).

The composition, morphology, and crystallographic microstructure of Al-Ti alloys electrodeposited from two different chloroaluminate molten salt electrolytes were examined. Alloys containing up to 28 % atomic fraction Ti were electrodeposited at 150 ?C from 2:1 AlCl3-NaCl with controlled additions of Ti2+. The apparent limit on alloy composition is proposed to be due to a mechanism by which Al3Ti forms through the reductive decomposition of [Ti(AlCl4)3]-. The composition of Al-Ti alloys electrodeposited from the AlCl3-EtMeImCl melt at 80 ?C is limited by the diffusion of Ti2+ to the electrode surface. Alloys containing up to 18.4 % atomic fraction Ti are only obtainable at high Ti2+ concentrations in the melt and low current densities. Alloys electrodeposited from the higher temperature melt have an ordered L12 crystal structure while alloys of similar composition but deposited at lower temperature are disordered fcc. The appearance of antiphase boundaries in the ordered alloys suggests that the deposit may be disordered initially and then orders in the solid state, subsequent to the charge transfer step and adatom incorporation into the lattice. This is very similar to the disorder-trapping observed in rapidly solidified alloys. The measured domain size is consistent with a mechanism of diffusion-controlled doman growth at the examined deposition temperatures and times.

AbstractThe adsorption behaviour of the herbicide clomazone on inorganic and organically modified montmorillonite from the Bogovina deposit in Serbia was investigated. Montmorillonite was modified first with NaCl and then with organic complexes such as hexadecyltrimethylammonium bromide (HDTMA) and phenyltrimethylammonium chloride (PTMA). Changes in the surface properties and morphology of the montmorillonite before and after the modification with various concentrations of organic complexes were investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Adsorption of clomazone on all examined samples was investigated using the batch adsorption method. Montmorillonite modified with HDTMA-bromide displayed greater uptake of the clomazone compared to the PTMA-montmorillonite, and both organically modified montmorillonites displayed greater uptake of the herbicide compared to the inorganic montmorillonite. Comparing the Freundlich coefficient and maximum adsorbed clomazone quantity values obtained by Langmuir model, the levels of adsorption of clomazone decreased in the following order: HDTMA-montmorillonite with 1.00 cation-exchange capacity (CEC) saturation > HDTMA-montmorillonite with 0.75 CEC saturation > PTMA-montmorillonite with 1.00 CEC saturation > PTMA-montmorillonite with 0.75 CEC saturation > HDTMA-montmorillonite with 0.50 CEC saturation > HDTMA-montmorillonite with 0.25 CEC saturation > PTMA-montmorillonite with 0.50 CEC saturation > PTMA-montmorillonite with 0.25 CEC saturation > Na-montmorillonite > raw sample. The type and content of an organic cation plays an important role in the behaviour of clomazone in a solid/liquid system. It is concluded that organically modified montmorillonite from Bogovina might be used as an effective adsorbent for clomazone.

The 370 Ma peraluminous South Mountain Batholith (SMB) intrudes Meguma Supergroup metasedimentary rocks in Nova Scotia. The New Ross area of the SMB contains polymetallic mineralisation (Sn, W, U, Mo, Cu and Mn) in pegmatite, greisen and vein directly or indirectly associated with highly evolved fractions of the SMB. Eight mineral deposits from this area have several fluid inclusion types hosted by quartz: (1) monophase liquid (L); (2) monophase vapour (V); (3) aqueous, L-V (4) aqueous, L-rich + solids; (5) aqueous, L-rich + halite. Inclusions have irregular to equant shapes and are pseudo-secondary or secondary. The irregularity and variability of L:V ratios within fluid inclusion populations suggest post-entrapment modifications of inclusions (i.e. necking).Thermometric data indicate three distinct fluids in terms of salinity: (1) 19-25 wt. % equiv. NaCl (rarely 14-25 wt. % NaCl equiv.), (2) 29-43 wt. % equiv. NaCl, and (3) 0-9 wt. % equiv. NaCl. Temperatures of first melting and ice/hydrohalife melting indicate CaCl2 in solution. Proximity of the deposits to Meguma Supergroup metasedimentary rocks suggests that this Ca component may be externally derived. The majority of the low-salinity fluid population has the composition of meteoric water. Electron microprobe analyses of artificially decrepitated mounds identify Na, Ca and K as major solutes, with a continuum in terms of compositions. Other solute components in the mounds are Fe and Ba, and a variety of metals of unknown speciation also occur (Cu, Zn, Fe, Ni). Homogenisation temperatures (Th) range from c. 80°C to 370°C, but for inclusion assemblages the range is 10°C to 20°C. Given the 3 kbar depth of emplacement of the SMB, estimated entrapment temperatures are c. 200°C to 550°C. The fluid inclusion data appear to reflect: (1) trapping of mixed Na-K-Ca brines during isobaric cooling in pegmatite and greisen deposits as indicated by large ranges in Th; (2) formation of deposits at different ambient pressures (i.e. depth); and (3) mixing of fluids of different reservoirs (i.e. magmatic, metamorphic, meteoric).

The Al-V alloys were synthetized by potentiostatic electrodeposition onto a glassy carbon electrode from equimolar AlCl3 + NaCl bath containing vanadium ions at 200 °C. The alloy deposits were characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy. The deposits were identified as Al3V and AlV3 alloys. It was found that intermetallic alloys were synthetized during aluminium underpotential deposition onto vanadium metal that was previously deposited on the glassy carbon electrode by diffusion-controlled overpotential deposition. Alloys were the result of solid-state interdiffusion between the initially deposited vanadium and the subsequently deposited aluminium. As a source to secure a constant concentration of vanadium in the electrolyte during deposition, vanadium anodic dissolution, and VCl3 melt addition were studied. The effect of vanadium ion concentration in the electrolyte on the composition and the surface morphology of the obtained deposits was investigated. The results indicate that controlled vanadium and aluminium codeposition could be a further step to the successful development of an advanced technology for Al3V and AlV3 alloy synthesis.

The Al-V alloys were synthetized by potentiostatic electrodeposition onto a glassy carbon electrode from equimolar AlCl3 + NaCl bath containing vanadium ions at 200 °C. The alloy deposits were characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy. The deposits were identified as Al3V and AlV3 alloys. It was found that intermetallic alloys were synthetized during aluminium underpotential deposition onto vanadium metal that was previously deposited on the glassy carbon electrode by diffusion-controlled overpotential deposition. Alloys were the result of solid-state interdiffusion between the initially deposited vanadium and the subsequently deposited aluminium. As a source to secure a constant concentration of vanadium in the electrolyte during deposition, vanadium anodic dissolution, and VCl3 melt addition were studied. The effect of vanadium ion concentration in the electrolyte on the composition and the surface morphology of the obtained deposits was investigated. The results indicate that controlled vanadium and aluminium codeposition could be a further step to the successful development of an advanced technology for Al3V and AlV3 alloy synthesis.

Films with Fe–25 at.% Ge composition are deposited by the process of laser ablation on single crystal NaCl and Cu substrates at room temperature. Both the vapor and liquid droplets generated in this process are quenched on the substrate. The microstructures of the embedded droplets show size as well as composition dependence. The hierarchy of phase evolution from amorphous to body-centered cubic (bcc) to DO3 has been observed as a function of size. Some of the medium-sized droplets also show direct formation of ordered DO19 phase from the starting liquid. The evolution of disordered bcc structure in some of the droplets indicates disorder trapping during liquid to solid transformation. The microstructural evolution is analyzed on the basis of heat transfer mechanisms and continuous growth model in the solidifying droplets.

Interpretation of seismic profiles and results of scientific drillings in the Mediterranean subseafloor provided indication of gigantic salt deposits which rarely crop out on land, such as in Sicily. The salt giants were ascribed to the desiccation, driven by the solar energy, of the entire basin. Nevertheless, the evaporite model hardly explains deep-sea salt deposits. This paper considers a different hypothesis suggesting that seawater reached NaCl saturation during serpentinization of ultramafic rocks. Solid salts and brine pockets were buried within the serpentinite bodies being later (e.g., in the Messinian) released, due to serpentinite breakdown, and discharged at seafloor as hydrothermal heavy brines. Therefore, sea-bottom layers of brine at gypsum and halite saturation were formed. The model is applicable to the Mediterranean area since geophysical data revealed relicts of an aged (hence serpentinized) oceanic lithosphere, of Tethyan affinity, both in its western “Atlantic” extension (Gulf of Cádiz) and in eastern basins, and xenoliths from Hyblean diatremes (Sicily) provided evidence of buried serpentinites in the central area. In addition, the buoyant behavior of muddled serpentinite and salts (and hydrocarbons) gave rise to many composite diapirs throughout the Mediterranean area. Thus, the Mediterranean “salt giant” consists of several independent geobodies of serpentinite and salts.

ZrAlYN films were prepared by magnetron sputtering at various N2/Ar flow ratio. The structure, composition and thermal properties were characterized by X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectrum. The results show that the deposited ZrAlN and ZrAlYN films possessed a single NaCl-type solid solution phase. The ZrAlN film was (200) strongly predominated. The (111) peak was prominently increased in ZrAlYN films and thus the preferred orientation changed to (111) and (200) co-predomination. The crystallinity of ZrAlYN films was gradually degraded with enhanced N2/Ar flow ratio. Both ZrAlN and ZrAlYN films were exhibited a featureless fracture microstructure. The thickness of ZrAlYN films was consistently reduced due to more nitride produced on the surface of targets at higher N2/Ar flow ratio. The ZrAlYN films deposited at 1:5 N2/Ar flow ratio was proved to be the best oxidation resistance under annealing at 1000°C for 2h in air. As N2/Ar flow ratio increased, the oxidation resistance of films was inversely deteriorated due to the decreased yttrium content in films.

Pulsed laser deposition (PLD) is a novel technique for the deposition of tribological thin films. MoS2 is the archetypical solid lubricant material for aerospace applications. It provides a low coefficient of friction from cryogenic temperatures to about 350°C and can be used in ultra high vacuum environments. The TEM is ideally suited for studying the microstructural and tribo-chemical changes that occur during wear. The normal cross sectional TEM sample preparation method does not work well because the material’s lubricity causes the sandwich to separate. Walck et al. deposited MoS2 through a mesh mask which gave suitable results for as-deposited films, but the discontinuous nature of the film is unsuitable for wear-testing. To investigate wear-tested, room temperature (RT) PLD MoS2 films, the sample preparation technique of Heuer and Howitt was adapted.Two 300 run thick films were deposited on single crystal NaCl substrates. One was wear-tested on a ball-on-disk tribometer using a 30 gm load at 150 rpm for one minute, and subsequently coated with a heavy layer of evaporated gold.

Thin films with a nominal composition close to Ti62.5Si37.5 were deposited on NaCl substrate at room temperature by pulsed laser ablation to study the evolution of the intermetallic compound Ti5Si3 using a combination of high-resolution and in situ transmission electron microscopy. The as-deposited amorphous films contain Ti-rich clusters, which influence the phase evolution and the decomposition behavior of the amorphous film. These clusters influence the nucleation of a metastable fcc Ti solid solution (ao = 0.433 nm) with composition richer in Ti than Ti62.5Si37.5 as the first phase to crystallize at 773 K. The Ti5Si3 nanocrystals form later, and even at 1073 K they coexist with fine fcc Ti-rich nanocrystals. Subsequent Ar+ ion-milling of the crystallized film results in a loss of silicon. The composition change leads to the dissolution of the Ti5Si3 nanocrystals and evolution of a new metastable Ti-rich fcc phase (ao= 0.408 nm).

Abstract. Laboratory experiments are presented on the phase change at the surface of sodium chloride–water mixtures at temperatures between 259 and 241 K. Chloride is a ubiquitous component of polar coastal surface snow. The chloride embedded in snow is involved in reactions that modify the chemical composition of snow as well as ultimately impact the budget of trace gases and the oxidative capacity of the overlying atmosphere. Multiphase reactions at the snow–air interface have been of particular interest in atmospheric science. Undoubtedly, chemical reactions proceed faster in liquids than in solids; but it is currently unclear when such phase changes occur at the interface of snow with air. In the experiments reported here, a high selectivity to the upper few nanometres of the frozen solution–air interface is achieved by using electron yield near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy. We find that sodium chloride at the interface of frozen solutions, which mimic sea-salt deposits in snow, remains as supercooled liquid down to 241 K. At this temperature, hydrohalite exclusively precipitates and anhydrous sodium chloride is not detected. In this work, we present the first NEXAFS spectrum of hydrohalite. The hydrohalite is found to be stable while increasing the temperature towards the eutectic temperature of 252 K. Taken together, this study reveals no differences in the phase changes of sodium chloride at the interface as compared to the bulk. That sodium chloride remains liquid at the interface upon cooling down to 241 K, which spans the most common temperature range in Arctic marine environments, has consequences for interfacial chemistry involving chlorine as well as for any other reactant for which the sodium chloride provides a liquid reservoir at the interface of environmental snow. Implications for the role of surface snow in atmospheric chemistry are discussed.

The focus of this work is on the evaluation of selected water quality indicators as per the applicable regulations, taking into account European and national legislation and the evaluation of the risk of contamination of surface waters with toxic elements using the contamination factor (Cfi) and the degree of pollution (Cd). The studied area of Slovinky is an important ore region, with rich deposits of copper and silver ores that have been mined for centuries. One of the most important remnants of mining activities in this area is the Slovinky tailing impoundment. The sludge pond area has an area of 15 ha, and the height of the dam is 113 m above sea level, which makes the sludge pond one of the tallest water structures in Slovakia. The Slovinský creek was monitored in the years 2010, 2011, and 2019 at five sampling points, which were selected to map the entire length of the water flow from the source to the estuary to the river Hornád. Risk elements (As, Cu, Cd, and Fe) and physicochemical parameters (such as temperature, dissolved oxygen concentration, conductivity, resistivity, salinity, total dissolved solids, NaCl, redox potential, and pH) were included in this study and evaluated according to applicable regulations, taking into account European legislation (Act No. 269/2010 Coll., guideline value WHO 2011). The results of the experimental studies showed that the highest values of As and Cu were measured at the site where drainage waters from the Slovinky tailing impoundment and mining water of the Alžbeta shaft flow into the creek. The concentration of As exceeded the limit value by up to 31 times and the concentration of Cu 16.8–134.5 times. At the same time, the highest values of conductivity, salinity, total dissolved solids, and NaCl were found, and there was no acidification of water at the site that had the highest pollution. Water contamination was assessed based on Cfi and Cd; our findings showed that the surface water from the site of contamination, along the entire length of the stream, was very highly contaminated with risk elements in the order of As > Fe > Cu, and the level of contamination decreased with distance from the site of contamination. Our research shows that seepage of toxic substances from sludge ponds and abandoned mines has caused the requirements for the quality of surface water of the Slovinský creek not to be met. In connection with mining activities, surface streams act as a transport medium through which other components of the environment can be polluted.

Metal displacement batteries (MDBs), or liquid metal batteries, are an emerging technology with significant potential in providing high capacity, low-cost energy storage solutions, capable of addressing many of the challenges associated with storing energy from renewable sources. The key characteristic of metal displacement batteries is that at least one of the electrodes is in liquid state and a molten salt is used as an electrolyte. Since its original proposal in the 1960’s liquid metal batteries have re-emerged in recent years and different battery chemistries and designs have been explored, including Ca-Bi, Na-Sb, and many others [2,10]. Recently, Na-Zn liquid metal batteries have been studied as an alternative to other configurations, showing significant potential in achieving good performance for large-scale energy storage, while avoiding the high cost associated with some electrode materials such as Nickel or Lithium [7,8]. In past years, alternatives to all-liquid cells have emerged in the form of designs where the cell materials are a mixture of solids and liquids. Examples of this include the commercially available Zebra battery, where a Na-NiCl electrode pair is used [1,6]. These designs offer some of the advantages of all-liquid cells, while simultaneously mitigating many of the disadvantages of handling and operating a very high temperature system. Na-Zn have also been proposed for solid cathode designs, taking advantage of the lower cost of Zn over Ni [4,3]. The cathode in these designs is composed of a porous structure, within which multiple chemical species can co-exist. Electrolyte components share the space with metal deposits,salt crystals, and other electrochemical reaction products. As a result, the micro-porous structure of this composite system is an important factor in determining the performance of the cell, as the spatial distribution of different materials can have an impact on the effective conductivity of the electrode [5,9]. The porous structure hosts complex multi-component mass transfer phenomena as well, potentially having an impact on the mass-transfer overpotential of the cell. This work aims to study the impact of the microstructural properties of the solid electrode in a liquid displacement battery, and their importance to the effective conductivity of the system. We have developed a computational tool that enables us to create randomized microstructures in 3D, representing the electrode-electrolyte assembly. We are able to preserve the desired physical characteristics by using target pore-size distributions and volume fraction input as seed parameters. We use this tool to generate representative structures and analyze their effective bulk conductivity by solving Laplace’s equation over the resulting domain, accounting for the different local conductivity of each material. This methodology is applied to a novel Na-Zn cell in order to assess the importance of the pore-scale properties of the cathode, as well as its material components, including solid Zn metal, solid NaCl deposits, and molten salt components. It is expected that different material arrangement configurations will induce heterogeneous current distributions in this system. Furthermore, the ionic composition of the electrolyte would be different at different charge levels, leading to additional variation through its charge/discharge cycle. Using this methodology, the range of different electrode phase configurations produced during operation can be studied in the absence of microstructure imaging data. A representative elementary volume for the Zn electrode assembly is analyzed to determine the best approach for up-scaled performance predictions of the Na-Zn cell. With this method, it is possible to acquire data to elucidate desirable or undesirable electrode structure properties of this system, providing insight which can be used for improving manufacture and operation of the cell. [1] Dustmann. “Advances in ZEBRA batteries”. J. Power Sources (2004). [2] Kim et al. “Liquid metal batteries: Past, present, and future”. Chemical Reviews (2013). [3] Lu et al. “An Intermediate-Temperature High-Performance Na-ZnCl2 Bat- tery”. ACS Omega (2018). [4] Lu et al. “Liquid-metal electrode to enable ultra-low temperature sodium- beta alumina batteries for renewable energy storage”. Nature Communications (2014). [5] Qiu et al. “Pore-scale analysis of effects of electrode morphology and electrolyte flow conditions on performance of vanadium redox flow batteries”. J. Power Sources (2012). [6] Sudworth. “The sodium / nickel chloride ( ZEBRA ) battery”. J. Power Sources (2001). [7] Xu et al. “Electrode Behaviors of Na-Zn Liquid Metal Battery”. Journal of The Electrochemical Society (2017). [8] Xu et al. “Na-Zn liquid metal battery”. Journal of Power Sources (2016). [9] Zhang et al. “Progress in 3D electrode microstructure modelling for fuel cells and batteries: transport and electrochemical performance”. Progress in Energy (2019). [10] Zhang et al. “Liquid Metal Batteries for Future Energy Storage”. Energy Environmental Science (2021). Figure 1

Recovery of energy from biomass and various waste–derived fuels by combustion has become important due to reduction of detrimental CO2 emissions. Biomass does, however, release significant amounts of chlorine and alkali metals, as e.g. HCl(g), KCl(g), KOH(g) and NaCl(g), into the gas phase during combustion. The alkali chlorides may cause deposits on superheater tubes, which interfere with operation and can lead to corrosion and/or blockage of the gas path. To prevent and diminish the problems mentioned above, better and more detailed knowledge of the reactions between potassium chloride and the tube materials during combustion is needed. These materials commonly contain, among other metals, chromium, which is thought to protect the rest of the material since it forms a very dense but thin oxide layer on the surface of the tube material. It has been suggested that the reaction between solid or partly molten KCl and chromium oxide is the one responsible for starting the complex series of corrosion reactions. In this work, the overall reaction between potassium chloride and chromium was studied through partial reactions with compounds known to participate to the overall reaction or to be formed during it. The reactions were studied in synthetic air by heating sample mixtures in a DTA/TGA (Differential Thermal Analysis/ Thermogravimetric Analysis) apparatus. Selected samples were also studied and analyzed with a scanning electron microscope equipped with an energy dispersive x-ray analyzer (SEM/EDXA). Under the used conditions both potassium chloride and potassium chromate reacted with pure chromium and chromium oxide. In the case of chromium, chromium oxide was formed via the formation of potassium chromate. In reactions including chromium oxide as reactant also potassium dichromate was detected.

Experimental studies were conducted to identify the physical and chemical features of gold’s behaviour in hydrothermal processes linked to ore formation and involving CO2 in oxidized deposits. With the aid of the autoclave method, in a temperature range of between 200 and 400 °C, the isochoric dependences of the PVT parameters of concentrated sulphate chloride fluids were plotted, both in the presence and absence of CO2. Our experiments established that concentrated sulphate–chloride fluids (22 wt % Na2SO4 + 2.2 wt % NaCl) that lack CO2 are characterized by a wide supercritical temperature range, with homogenization temperatures of between 250 and 325 °C. In the presence of CO2, the same type of fluids showed heterogenization at a molar fraction of XCO2 = 0.18 (t = 192 °C, P = 176 bar). The process of homogenization for these low-density and high-salinity fluids was impossible at temperatures between 375 and 400 °C and at pressures between 600 and 700 bar. The behaviour of gold was studied during its interaction with a basic composition fluid of sulphate–chloride. We applied the autoclave method under the conditions of a simultaneous synthesis of pyrite and gold dissolution (metallic Au), at a temperature of 340 °C and at a pressure of 440 bar. High Au concentrations (up to 4410 ppm of Au in CO2-bearing fluids) were attained at high gold solubilities (up to 13.5 ppm in the presence of CO2), owing to the process of Au reprecipitation within the pyrite phase. We did not detect Au in the pyrite when we used the XRD or SEM methods, which suggested that it might be present as invisible gold. High values of the distribution coefficient (KD = CAu(solid)/CAu(solution)) in the fluids lacking (KD = 62) and bearing CO2 (KD = 327) empirically confirmed the possibility that gold concentrates in pyrite in structurally non-binding forms.

AbstractCarbonatites are enriched in critical raw materials such as the rare-earth elements (REE), niobium, fluorspar and phosphate. A better understanding of their fluid regimes will improve our knowledge of how to target and exploit economic deposits. This study shows that multiple fluid phases penetrated the surrounding fenite aureole during carbonatite emplacement at Chilwa Island, Malawi. The first alkaline fluids formed the main fenite assemblage and later microscopic vein networks contain the minerals of potential economic interest such as pyrochlore in high-grade fenite and rare-earth minerals throughout the aureole. Seventeen samples of fenite rock from the metasomatic aureole around the Chilwa Island carbonatite complex were chosen for study. In addition to the main fenite assemblage of feldspar and aegirine ± arfvedsonite, riebeckite and richterite, the fenite contains micro-mineral assemblages including apatite, ilmenite, rutile, magnetite, zircon, rare-earth minerals and pyrochlore in vein networks. Petrography using a scanning electron microscope in energy-dispersive spectroscopy mode showed that the rare-earth minerals (monazite, bastnäsite and parisite) formed later than the fenite feldspar, aegirine and apatite and provide evidence ofREEmobility into all grades of fenite. Fenite apatite has a distinct negative Eu anomaly (determined by laser ablation inductively coupled plasma mass spectrometry) that is rare in carbonatite-associated rocks and interpreted as related to pre-crystallization of plagioclase and co-crystallization with K-feldspar in the fenite. The fenite minerals have consistently higher midREE/lightREEratios (La/Sm ≈ 1.3 monazite, ≈ 1.9 bastnäsite, ≈ 1.2 parisite) than their counterparts in the carbonatites (La/Sm ≈ 2.5 monazite, ≈ 4.2 bastnäsite, ≈ 3.4 parisite). Quartz in the low- and medium-grade fenite hosts fluid inclusions, typically a few micrometres in diameter, secondary and extremely heterogeneous. Single phase, 2- and 3-phase, single solid and multi solid-bearing examples are present, with 2-phase the most abundant. Calcite, nahcolite, burbankite and baryte were found in the inclusions. Decrepitation of inclusions occurred at ∼200°C before homogenization but melting-temperature data indicate that the inclusions contain relatively pure CO2. A minimum salinity of ∼24 wt.% NaCl equivalent was determined. Among the trace elements in whole-rock analyses, enrichment in Ba, Mo, Nb, Pb, Sr, Th and Y and depletion in Co, Hf and V are common to carbonatite and fenite but enrichment in carbonatitic type elements (Ba, Nb, Sr, Th, YandREE) generally increases towards the inner parts of the aureole. A schematic model contains multiple fluid events, related to first and second boiling of the magma, accompanying intrusion of the carbonatites at Chilwa Island, each contributing to the mineralogy and chemistry of the fenite. The presence of distinct rare-earth mineral microassemblages in fenite at some distance from carbonatite could be developed as an exploration indicator ofREEenrichment.

The application of amorphous alloys as thin-film coatings with good corrosion properties has drawn attention in the last years since overcoming the typical limitations of these materials, such as the critical size and brittleness. Techniques based on Physical Vapor Deposition, like DC magnetron sputtering, are interesting once it allows parameter optimization to achieve the desired microstructure [1,2,3]. This study aims to characterize the electrochemical properties of a novel FeCrMoNbB (low Cr content – 11at%) alloy as a coating. Thin-film coatings were produced in a DC magnetron sputtering PVD system with 0.5 Pa Ar working pressure, 92 W of sputtering power, and 200°C deposition temperature. The substrate was 316L stainless steel. Corrosion tests were performed in a three-electrode cell in a Gamry 600+ potentiostat using the following sequence: two hours of open circuit potential (OCP), electrochemical impedance spectroscopy (EIS) from 100kHz to 0,02 Hz, 20 minutes of OCP, and potentiodynamic polarization test from -0,03 to 1,2V (vs. OCP). The solution was a 0,6M NaCl (Cl- content equivalent to seawater), natural pH of 5.5. Measurement Model software, developed by Orazem et al. [4], was used for data regression. X-ray photoelectron microscopy (XPS) was performed to obtain complementary information about the passive film. An XR3E2 apparatus from Vacuum Generator with an Mg-Kα source was used. The analysis was performed after stabilization in an open circuit for two hours. Fully amorphous thin films of about 400 nm were obtained. Outstanding corrosion behavior was observed for the coating, which presented a corrosion current (icorr) around 5 x10-9 Acm-2 and a corrosion potential of 127 mV. The icorr value is more than two decades lower when compared to the 316L of the substrate, indicating a higher corrosion resistance after applying the coating. EIS results showed a high impedance modulus at low frequency was |Z|LF = 3.7 MΩ.cm2. XPS analysis showed that all the alloying elements were in the oxidized form on the surface. Metallic species from the underlying surface could also be detected, meaning the oxide layer has less than 10 nm. Regression with Measurement Model software found a global capacitance C = 5.7 μF.cm2, a typical value for a compact passive layer. From the value of C, the film thickness was estimated to be around 2 nm, corroborating with the XPS analysis. A compact, thin layer of oxide composed of Cr, Nb, and Mo can be associated with high protectiveness of the passive film, hence, good corrosion resistance. Furthermore, the pitting phenomenon typical of 316L near 500mV was not observed in the coating. In summary, the results are promising for using these alloys as coatings for marine applications, potentially replacing conventional stainless steels. [1] M. Panayotova, Y. Garbatov, C. Guedes Soares, Corrosion of Steels in Marine Environment, Monitoring and Standards, Safety and Reliability of Industrial Products, Systems and Structures, Taylor & Francis Group, 2008.p.370. [2] WOOD Maureen; VETERE ARELLANO Ana Lisa; VAN WIJK Lorenzo. Publications Office of the European Union; 2013. JRC84661 [3] Chu, J. P. et al. Thin film metallic glasses: Unique properties and potential applications. Thin Solid Films 520, 5097–5122 (2012). [4] M.E.O. W. Watson, EIS: Measurement Model Program., ECSarXiv. (2020). https://doi.org/10.1149/osf.io/kze9x.

Summary A total of 41 chalk core plugs, cut with the same orientation from large blocks of outcrop chalk, have been aged in crude oil at 90 °C for different time periods, in duplicate sets. Different filtration techniques, filtration temperatures and injection temperatures were used for the crude oil. Oil recovery by spontaneous, room temperature imbibition, followed by a waterflood, was used to produce the Amott water index for cores containing aged crude oil and for cores where the aged crude oil was exchanged by fresh crude oil or decane. The main objective was to establish a reproducible method for altering the wettability of outcrop chalk. A secondary objective was to determine mechanisms involved and the stability of the wettability change. The aging technique was found to be reproducible and could alter wettability in Rørdal chalk selectively, from strongly water-wet to nearly neutral-wet. A consistent change in wettability towards a less water-wet state with increased aging time was observed. Introduction Wettability is defined as the tendency of one fluid to spread on, or adhere to, a solid surface in the presence of other immiscible fluids (Ref. 1). Wettability is a major factor controlling the location, flow, and distribution of fluids in a reservoir. Hydrocarbon recovery results from a combination of capillary and viscous forces and gravity. In most chalk reservoirs spontaneous imbibition is the major recovery mechanism. This dominance of capillary forces is due to narrow pore throats, more or less water-wet conditions, and the low permeability of this rock. Thus the wettability is a very important parameter controlling the capillary pressure (Refs. 2, 3). However, wettability is not an explicit parameter in the equations that describe flow in porous media and the effects are therefore reflected by the change in capillary pressure and relative permeability (Ref. 4). The literature (Refs. 1, 5-7) reports that polar components in the crude oil (CO), like resin and asphaltene groups, may alter the wettability of porous rock. These oil components can adsorb on the rock surface by different mechanisms including polar, acid/base, and ion-binding interactions (Ref. 7). Oil composition, surface rock mineralogy, history of the fluids exposed to the rock surface, pore roughness, water saturation, and water composition (Refs. 1-10) are all critical parameters affecting wettability alteration. However, the influence from each parameter on wettability is not well known and may well involve synergistic interactions. This study was initiated by the need to quantitatively assess the relative importance of the forces acting during waterflooding fractured chalk blocks at different wettabilities (Ref. 11). A series of experiments were conducted at water-wet conditions which investigated spontaneous axial imbibition in stacked cores and the impact of fractures on hydrocarbon displacement mechanisms for large chalk blocks. During this study a dynamic in situ, nuclear tracer imaging technique was used to track the water advancement (Refs. 12,13). In addition the scaling of oil recovery by spontaneous imbibition in cores of various lengths and areas of the exposed faces to brine, i.e., one- (1D), two- (2D), and three-dimensional (3D) exposure, and the gravitational effects on vertically stacked cores have been investigated (Refs. 14-18). To extend this study to relevant reservoir conditions experiments have been performed to alter wettability of outcrop chalk and produce a porous rock which mimics the reservoir rock during laboratory studies (Ref. 5). In this paper we describe reproducible ways of altering the wettability in low-permeable outcrop chalk. The methods most often used to measure wettability in core plugs are the Amott test (Ref. 19) and the United States Bureaus of Mines (USBM) method (Ref. 20). In this paper the Amott wettability index for water together with the imbibition rate will be used to characterize the wettability of the cores. Both the Amott test and the USBM method only give one parameter to characterize the average wettability of the cores. Both methods have serious weaknesses with respect to discriminating between different wettabilities in a certain range of wettability (Ref. 21). Lately a new test has been proposed where the early imbibition rate was used to determine the core wettability (Ref. 9). Experiment The Rørdal chalk used in this study was obtained from the Portland cement factory in A°lborg, Denmark. Core data for the outcrop chalk is found in Table 1. The rock formation is Maastrichan age and consists mainly of cocolitt deposits (Ref. 22) with about 99% calcite and 1% quartz. The brine permeability and porosity for the Rørdal chalk cores ranged from 1-4 mD and 45-48%, respectively. All the core samples were drilled in the same direction from large chalk blocks to obtain analogous material and to ensure the same orientation relative to bedding planes or laminations. The chalk cores were dried at 90 °C for at least seven days before being used. The composition of the brine was 5 wt. % NaCl+5 wt. % CaCl2. CaCl2 was added to the brine to minimize dissolution of the chalk. Sodium azide, 0.01 wt. %, was added to prevent bacterial growth. The density and viscosity of the brine were g/cm3 and 1.09 cP at 20 °C, respectively. The brine was filtered through a 0.45 µm paper filter membrane. The salts used in the brine were: NaCl obtained from Phil Inc. with a purity of 99.5%, CaCl2 obtained from Phil Inc. with a purity of 99.5%. Sodium azide had a purity of 99.5%. The materials were used as received. The physical properties of the fluids are summarized in Table 2. A North Sea stock tank crude oil was used to alter the wettability of the Rørdal chalk cores by aging; i.e., submersing cores in the crude oil at elevated temperature for various length of time. Crude oil composition was measured to 0.90 wt. % asphaltenes, 53 wt. % saturated hydrocarbons, 35 wt. % aromatics, and 12 wt. % nitrogen-sulphur-oxygen containing components (NSO). The acid number was measured at 0.094 and the base number at 1.79.

Biosurfactants are natural substances produced by several bacterial and fungal organisms that are amphiphilic and are extracellular (a part of the cell membrane). Biosurfactants can reduce the stress between solids and liquids on the surface and at the end. Biosurfactants have several properties, i.e. they are stable, less harmful, as well as readily degradable, and extremely eco-friendly. Biosurfactants also have a wide range of industrial uses because they are a versatile category of chemical substances. The principal justification for conducting such research was the isolation of possible biosurfactants containing bacteria. Sampling was performed for the isolation of bacteria producing biosurfactants from different oil-polluted sites That is to say, experiment for emulsification, test for oil spreading, test for drop collapse, and measure for hemolysis. The capability to produce biosurfactants was seen in 22 different isolates from polluted sites B1, B2, and B3. Through different biochemical tests and Gram staining, it was identified that isolated bacterial strains are Pseudomonas spp and that is Pseudomonas aeruginosa. The procedure used as characterizing biosurfactants was the TLC plate’s procedure, by using TLC plates process yellow dots emerged after spraying on silica gel plates with an throne and ninhydrin reagents. These yellow spots confirmed the presence and production of rhamnolipid in the biosurfactant. Hence, it was concluded that identified strains in the study can be helpful in the heavy metals, pesticides, and hydrocarbons bio-degradation and bioremediation. These may also be used as biological control agents to protect plants from various pathogens, resulting in improved crop yields. Introduction Biosurfactants are natural substances produced by several bacterial and fungal organisms that are amphiphilic and are extracellular (a part of the cell membrane) (Chen et al., 2007; Ghayyomiet al., 2012). Main purpose of the bio-surfactantsgeneration or production is a consequence of financial availability (Van Dyke et al., 1993 It is reported that almost 50 percent of the world's surfactants are used because of the need for cleaning agents as well as the rate of growth grows every day (Deleu and Paquot, 2004). Appropriate use of bio-surfactants will control environmental emissions what these are the most dangerous, constantly rising gradually and disrupting the routine maintenance of life every day. Awareness campaign initiatives have been introduced and also increase for environmental laws, various innovative approaches need to be implemented and even the issue of pollution focused entirely. Developing appropriate advanced technologies to help clear up chemicals and toxins from the ecosystem, like hydrocarbons (both inorganic and organic). Studies on biosurfactants are being launched by scholars and researchers with significant health issues like adverse environmental effects, air contamination, environmental change, and waste management (Makkar and Cameotra, 2002 Biosurfactants contribute to expanded demand for such microbial products as alternatives to chemical surfactants (Benatet al., 2000). Microbes seem to have the capability to degrade contaminants, but their biodegradation is limited leading to hydrophobicity, low solubility in water, and inadequate bioavailability, of such pollutants (Patil, et al., 2012). GhayyomiJazeh, Mishraet. al (2001) those bacteria that produce biosurfactants were isolated from the site of petroleum spills and afterward, 160 strains and as well as 59 strains were able to produce biosurfactants have shown better performance in a test for hemolysis of blood, and 45 strains with positive findings within oil spread experiment were applied in the laboratory to isolate and segregate the media cultured Banat process (Rahman et al., 2002) These were observed and researched that biosurfactants of Pseudomonas aeruginosa spp are most likely to disrupt the bonding of hydrocarbons like nonadecane, octa, Hexa, and hepta, in marine Water contaminated with oil spills up To approximately 47%, 53%, 73% and 60%(Abrar et al., 2020). Current study concluded that the isolated strain having the ability to degrade hydrocarbon as well as the ability to degrade the heavy metal. The strain also can protect the plant from various diseases. The present research found that the isolated strain is capable of degrading hydrocarbon while also being capable of degrading the heavy metal. As well as the strain does have the capability to defend plants from different diseases. Material And Methods Area of Study The investigation was conducted at HazaraUniversity(HU) Microbiology Laboratory, MansehraPakistan. Assemblage of Samples Thehomestay area of the city Mansehra Pakistan which is named as a township, where oil spills arose, oil spills soil samples were obtained as well as sampling from various Mansehra automobile workshops were also done. Sterilized bags of polythene were being used to collect samples of the soil, after thatthe sample was taken towards the Hazara University (HU) Mansehra Microbiology Laboratory to examine and extract bacterial strains that could develop biosurfactants. The soil temperature at the time of sample selection was around 30 ° C. The pH was also verified by Galvano science companies at the time of selection by pH meter, and the pH being reported was 7. Preparation of Media 15 x 100 mm Petri dishes were being used to prepare the media. Agar plates were thoroughly cleaned with water from the tap and then carefully covered in aluminum foil following cleaning then placed within autoclave at 121°C for about 15 min at 15 psi for sterilization. The nutrient agar which contains 0.5% NaCl, 0.3% beef extract, 0.5% peptone, and 1.5% agar, in 500 ml of distilled water, 14 g of the nutrient agar media (Merck) were dissolved. The nutrient level used mainly for the production of non-fastidious species. Nutrient agar is widely known as it's capable of growing a variety of bacteria types and provides nutrients required for the growth of bacteria. Upon sufficient dissolution of such nutrient agar in distilled water, these were then sterilized by autoclaving for 15 min at 15 psi in the autoclave and held at 121 °C Upon autoclaving, pouring of the media was done in laminar flow hood, and then packed and placed for yet more use in a fridge at 4°C. 2.4 Preparation of serial dilution The bacteria are isolated using the serial dilution process. During this process, 10 test tubes were taken and distilled water (9ml) was added in each tube. After that tubes were put for 15 minutes in the autoclave machine at 121°C. After that 1gm of a crude oil sample from the soil was added in a test tube containing distilled water. Further, 1 ml of the solution was taken from the first test tube and poured to the adjoining tubes for the preparation dilution as under . Afterward, 10μl of the solution was pipetted from both the dilution of and shifted for spread culture techniques, then incubated the plates at 37°C for 48hrs. Biosurfactants extraction Firstly, in nutrient broth solution theculture of bacteria was added and inoculated with oil, the bacterial colony was then incubated at the temperature of 25°C in a shaking incubator just for 7 days. Incubation after seven days of trembling. Thebacterial Crop was then taken and centrifuged at 5000rpm at temperature 4°C for 20minutes. Following centrifugation, the supernatant was collected and then mixed in the equivalent amount in Methanol: Chloroform. White sediment was then retained and collected for further use . Bacterial Colonies Isolation 1 g of the soil polluted with oil was diluted serially up to 106 dilutions.10 μl of 104 and 106 dilutions for spread culture were transferred to the MSM agar plates and nutrient agar. The plates were then incubated at 37°C for 48hrs. Twenty-two morphologically separate colonies were separated for further specific examination just after the incubation and processed by using the technique of streak plate. Screening of Isolates’ Biosurfactants Behavior To check the activity of biosurfactants produced by the bacterial species the following methods of screening were done. Hemolytic Activity of Biosurfactants for Erythrocytes Blood agar containing 5% of blood was prepared as after the fresh isolates were added and inoculated on blood agar plates, then the plates were taken and placed in the incubator at temperature 37°C for 48hrs (Rashediet al., 2005). Thereafter the observation of clear zone in the colonies indicated the existence of bacterial species that produce biosurfactants. This experiment was undertaken to control the ability of isolated bacteria to induce blood agar hemolysis. Three forms of hemolysis usually involve; alpha, beta, and hemolysis of the gamma. The agar underneath the species is dark greenish, then it is Alpha, the yellowish color produced in beta hemolysis and gamma hemolysis does not affect the bacterial sppwhichadded on the plates (Anandaraj and Thivakaran, 2010). Bio-surfactant identification with process of CTAB MSM (Mineral salt agar medium) with (2%) of glucose serving both as carbon source, (0.5 mg / ml) acetyl-tri-methyl-ammonium-bromide (CTAB), and methylene blue (MB: 0.2 mg/ml) are used to detect anionic bio-surfactants (Satpute et al., 2008). For this method, thirty microliters (30μl) of cell-free supernatant were added to each of the wells of the methylene blue agar plate that comprises of borer (4 mm in diameter). after that, the incubation of the plates was done for 48-72 hrs at 37°C. Just after incubation in each of the wells, a dark blue halo zone was being used to show the successful anionic bio-surfactant production. Table 1: Composition of MSM Media S. No Ingredients Amount (gm/L) I Potassium dihydrogen phosphate (KH2PO4) II Magnesium Sulfate (MgSO4) III Iron Sulfate (FeSO4) IV Sodium Nitrate (NaNO3) V Calcium Chloride (CaCl2) VI Ammonium Sulfate (NH4)2SO4 Technique for Spreading of Oil A sufficient number of isolated bacteria were inoculated into a solution of 100ml nutrient broth. Over 3 days, the culture was incubated at 37 ° C in a rotating shaker incubator (150 rpm). After that biosurfactants synthesis was checked in culture suspensions (Priya and Usharani, 2009; Anandaraj and Thivakaran, 2010). For this process, thirty milliliters (30ml) of distilled water was added in a Petri dish. In the middle of the distilled water, 1 milliliter (1ml) of diesel oil was added, and then a centrifuged twenty microliter (20μl) culture was introduced to the middle of a plate, which was isolated from oil spilled soil or local oily groundwater. The species producing the bio-surfactant displace the hydrocarbons and disperse it even in the water. Then it was calculated and analyzed within 1 mint (Ali et al., 2013). Technique for Drop collapse In this process, 96-wellsformed in each of the plates of nutrient agar. Afterwards, all the 96-wells of microliter plates was then filled withmineral oil of about 2ml. Then stabilized the plate at 37oC for 1 hour, after which the oil surface was filled with 5μl of supernatant culture. Therefore, the drop shape was taken to be observed on the oil surface after 1min. The drop which was collapsed, generated by the supernatant culture which is used to signify positive(+ive) outcome and the drops which stayed the same and displayed no changeindicates negative(-ive) outcome. And was taking distilled water as a control(Plaza et al., 2006). Emulsification index The emulsification index was calculated, as stated by the process followed by Cooper and Goldenberg (1981) In this process, 2 ml of kerosene oil was taken and inserted in each of the test tubes to the same amount of cell-free supernatant, and then homogenized for 2 min in a vortex at high speed and allowed for 24 hours to stand. The emulsification steadiness was then determined after the 24 hours, and the emulsification value was estimated by measuring the emulsified layer height by the total liquid layer height, then multiplied by 100. Quantification for the Dry weight of Biosurfactants The bacterial colony was inserted and inoculated in the nutrient broth medium, followed by oil and centrifuged at 5000rpm and after that, the supernatant was clutched and treated with chloroform and methanol and mixed. The white colored deposits were taken and used for the furtherprocess of dry weight. Afterwards, took the clean Petri plate and determined the empty plate weight. Next, the sediment was poured onto Petri plates. Now, for the drying process the hot air oven was used and set the 100ºC of temperature for 30minutes and the plates were put in the oven. After the drying process, the plates were weighted again. The dry weight was calculated for the biosurfactants using the formula which described below: Selected strains Identification and their characterization Instead, various basic biochemical methods were used to identify the isolated bacterial strains. Various biochemical tests, such as Gram staining, Oxidase test, Urease test.Catalase test, Methyl red test, Motility test, Indole test, Starch hydrolysis, Citrate test, Spore staining, Gelatin hydrolysis. Then afterwards, for the preliminary characterization of the biosurfactant, the thin layer chromatography process was used. Physical characterization of the strains selected Gram staining First, on the slide, using the wire loop the bacterial pure culture was taken, and smear was prepared on the slide, and then a drop of purified water was applied. Then, the sterile loop or needle was correctly mixed the bacterial colony and purified water, then mixed up until it is somewhat turbid. Then, spirit lamp was used to fixed the bacterial smear on slide and cooled to room temperature. With this glass slide was loaded with solution of crystal violet and stood for 1minute anddistilled water was applied on slide. Meanwhile the slide was submerged for 1 minute with the iodine solution, and then flushed and rinsed with water. Therefore, decolorizer of about 1 to 2 drops(5 percent acetone and 95 percent alcohol) were added to the slide’s smear and stand for 30seconds, and then treated with water. After then slide was rinsed with safranin for 60seconds, and then treated with water anddry in air. Microscopic analysis was done with 100x objective lenses using emersion oil on smear. Cell morphology The isolates of the bacterial cell were gram stained on slides and then the slides were observed under the light microscope, showing the shape and color of the cells. Biochemical characterization of the selected strains Catalase test Aim of this study is to identify, evaluate and examine that, whether or not the microbes are capable of producing catalase enzymes, while catalase is a protective enzyme, i.e. catalase has the potential to protect against the lethal chemicals known as (H2O2). In this study a bacterial culture that was clarified overnight was used. This culture has been smeared on a glass slide, and 3 percent hydrogen peroxide (H2O2) has been applied and observed on smear. Effects have been observed for bubble formation. Citrate test This study was performed to check the amount or ingest the citrate as the carbon and energy supply for growth and metabolism. Medium containing bromothymol blue and sodium citrate as pH indicator, bacterial was introduced. Ammonium chloride is also present in this medium used as a nitrogen source. Results were noted with variations of color from green to blue. Urease test The capability of urease enzyme for degrading urea was calculated in this bacterial capacity test. Bacterial culture was taken and inoculated for 48 hours at 37 ° C in urease broth, and then color was observed. Methyl red test Through using the process known as mixed acid fermentation which is used to evaluate the bacteria's acid production. The bacterial culture was taken and introduced in the broth of MR-VP and then incubated for 3days at a temperature of 37°C. Two (2) to three (3) drops of Methyl red were added in the broth medium after the incubation period. The change in broth color was observed for final results after a few seconds. Indole test Through using the process to assess the bacteria 's capability to crash indole from tryptophane molecules. After the 24 hours of incubated, taken the fresh inoculum of bacteria and then inserted into the tryptone medium, 24 hours of incubation of about 30oC, 2ml of the tryptone broth medium was added into a sterile test tube. Kovac's reagent was taken to be added (few drops) in sterile test tube and stimulated for a few minutes, and variations of color were detected. Gelatin test It is the approach assess to figure out the use of enzymes known as gelatins from bacterial organisms that precipitate the gelatin. Fresh inoculum of bacteria was taken after 24 hours, and inserted into the media of gelatin agar. This was incubated for around 24 hours, so the temperature did not exceed 30 ° C. Media was observed after incubation time. Starch hydrolysis Several of the micro-organisms that use the starch as a carbon energysource. Therefore, this method has been used to assess whether or not bacteria may use starch as a source of carbon. The bacterial fresh inoculum was spread on the petri starch agar plates, and after that the plate was incubated for 24 hours andmaintained the temperature at 30 to 35 ° C, then gradually applying the supplements of iodine to the plates to flow the change, and then examining the plates. Preliminary characterization of the strains selected Experimental characterization of the bio-surfactant was performed by using the process of TLC (Anandaraj et al., 2010). On a silica gel plate, crude portion of the rudimentary bio-surfactant was separated using Methanol: Chloroform: water (CH3OH: CHCl3: H2O) in the ratio of as an eluent with a different color producing reagents. Ninhydrin reagent (0.5 g ninhydrin in 100ml anhydrous acetone) was used to find bio-surfactant lipopeptide as red spots and anthrone reagent (1 g anthrone in 5ml sulfuric acid combined with 95ml ethanol) as yellow spots to identify rhamnolipid bio-surfactant (Yin et al., 2008). Results and Discussion Isolation of bacteria At first, twenty-two (22) strains from a polluted soil sample were isolated from nutrient agar media.Mixed culture provided by these colonies, so they were taken and smeared on the plates of nutrient agar and then fresh inoculum was collected and stored at temperature of 4oC for the further analysis. Bio-surfactants (surface-active compounds)are formed by a variety of amphiphilic bacterial and fungal organisms that are extracellular (a part of the cellular membrane) (Chen et al., 2007). Screening of Isolated strains for biosurfactant producing colonies Different experiments were carried out to identify, isolate and screen bacteria that are capable of generating bio-surfactants and that is Oil spreading technique(OST), blood hemolysis test(BHT), CTAB test, Emulsification operation. There were twenty-two distinct isolates observed in the current research. And the B1, B2 and B3culture were taken and selected from the twenty-two (22) strains isolated from the polluted spot, which were found to produce biosurfactant. And the oil spreading technique showed promising results for these strains. And strain B2 showed a greater displacement of oil and this is 4 mm. Oil spreading method is quick and often easy to handle, and this technique requires no particular equipment, only a very small amount of sample is used. This approach can be applied when the production and quantity of biosurfactant is small (Plaza et al., 2006) and (Youssef et al., 2004) Only bacterial cultures have been allocated and screened for bacterial species that can generate or use biosurfactants. Just three (3) strainsamong them presented the best results.Those 3 strain,s (B1, B2 and B3) were selected as an additional analysis. Blood hemolysis test On the petri plates of blood agar, the . Isolated bacteriaof B1, B2 and B3 were taken andstreak at the temperature about 37°C for 48 hours. Strain B1 demonstrated β (Beta) hemolysis after the incubation cycle and B2 and B3strains demonstrated γ (Gamma) hemolysis. The B1 strain had an emulsification index of about 74 percent and that was very high as compared to 70 percent for B2 and about 53 percent for B3 respectively. Around the same time, B1 strain showed β (Beta) hemolysis and γ (Gamma) hemolysis was shown bystrains B2 and B3 on the platesof bloodagar. The β hemolysisshowed by the strain B1 in the blood agar test, and the strain B2 and B3 showed γ (Gamma) hemolysis. It is determined that 20 percent strains that are the bestproducer of rhamnolipid have not fully lysed the blood, because the ability of the producer strains capacity not be responsible for the hemolytic activity. According to many researchers, who have shown that this is not such an effective tool for biosurfactant detection due to many bioproducts that may also induce red blood cell lysis, that is not so sufficient to be the surface-active molecule (Youssef et al., 2004). (Rashedi and others, 2005). Table2 Blood Hemolysis Test CTAB agar plate test This test confirms the anionic biosurfactants development. After plate incubation at a temperature of 37 ° C for 72 hours, dark blue hollow zone was existedaround each of the B1 strains wells, which clearly indicated the positive (+ive) development of anionic Biofactant. In addition, the B1 and B2 strains showed positive (+ I ve) results and, in the CTAB analysis, the B3 strain was found to be negative (-ive). The growing microorganisms when secreted the anionic biosurfactants on the plates of CTAB (cetyl-tri-methyl-ammonium-bromide) and methylene blue, then as a result the dark blue-purple insoluble ion pairs formed on the plates. The halo zone around each of the colonies was developed that can recognize rhamnolipid production and that was dark blue in colour, and could correlate with production of rhamnolipid (Siegmund et al., 1991). As indicated in (Fig1) Fig1: B1 positive on CTAB agar plate Oil Spreading Technique The oil was displaced by B1, B2and B3 strains in this test strain and showed a zone that was so clear. The bacterial strains capable of developing biosurfactant were tested and separated from the sample of soil which was oil spilled and brought from the District of Mansehra, Pakistan and from automobile workshops of Mansehra. As shown in (Fig.2). Fig.2: Results of Oil Spreading by B1, B2 and B3Table 3;.Test for oil spreads Bacterial culture Formation of zone (mm) Readings B,1 B,2 B,3 Drop-collapse technique During this process the drop shape was observed at the oil surface. As seen in Fig 3, the collapsed drop was provided by the supernatant culture B1 , B2 and B3.. Emulsification index Emulsification stability was measured with the use of kerosene oilin this test, and then observed the results. Since this emulsification index was calculated by dividing the height of the emulsion layer by the total height of the liquid layer and then multiplying by 100, as shown in the formulation below. Emulsification index Emulsification stability was measured with the use of kerosene oilin this test, and then observed the results. Since this emulsification index was calculated by dividing the height of the emulsion layer by the total height of the liquid layer and then multiplying by 100, as shown in the formulation below. Fig 3: Result of Drop-collapse test Table 4: The activity of Biosurfactant emulsification Dry weight of bio-surfactants In this examination, white-colored sediment was collected. Then measured the weight of the sterile Petri plate which was empty in the first step. Then, the sediment was poured into plates. The plates were taken and weighted after 30 minutes of drying on a hot air oven, following the process of drying. The weight of biosurfactants (dry weight) was measured using the following formulations: Fig 4: Dry weight of biosurfactants Table: 5: Dry weight of the biosurfactants Bacterial Culture Weight of the plate (g) biosurfactant in The plate after drying (g) Dry weight of Biosurfactant (g) B,1 B,2 B,3 Identification of selected strains and their characterization Gram staining For structural applications, and stroke analysis gram staining method was used.(Fig.5) shows findings from the process of gram staining. Fig 5: Microscopic view of Gram staining Biochemical identification of bacterial strains and their characterization Specific biochemical studies were performed to identify the species for further recognition and characterization. The bio-surfactant producing microorganism was found to be Pseudomonas aeruginosa after conducting various characterizations and the biochemical tests(Eric Deziel et al., 1996), Which can be used to further analyze and study the industrial development of the biosurfactant. Rhamnolipid is also isolated and produced from the Pseudomonas aeruginosa species on the silica gel plate (Rashedi et al., 2005), a form of biosurfactants highly recommended for processes of bioremediation. All the findings collected from biochemical testing were labeled as Berge 's Manual and it revealed that the protected microorganism was (Pseudomonas aeruginosa). Results of biochemical test were tabulated in (Table.5) Table 6: Bacterial strain identification Tests B1 B2 B3 Gram staining Negative Negative Negative Oxidases Positive e Positive Positive Catalase Positive Positive Positive Indole Positive Negative Negative Citrate Positive Negative Negative Urease Negative Positive Negative Nitrate Positive Positive Positive Motility Positive Positive Positive Gelatin hydrolysis Positive Negative Negative Lactose Negative Positive Positive Methyl red Negative Positive Positive Voges Proskauer Negative Negative Negative Fig 6: Results of biochemical tests(A) Methyl red and Voges Proskauer tests (b) catalase tests (c) oxidase tests (d) indole tests (e) citrate tests (g) lactose tests (h) urease tests Preliminary bacterial strain’s characterization The plates showed yellow dots, when sprayed with anthrone reagent. It indicated the existence of biosurfactants of rhamnolipid in the organism on the plate of TLC as seen in theFig.7 Fig 7: Biosurfactant characterization by TLC Conclusion Biosurfactant development is exciting and perceptible across industries to clean up oil waste and pollutants, particularly in the ecosystem.Compared with chemical surfactants, the biosurfactants are less harmful. It plays an important role in defining the advantages and the importance of industrial applications. Therefore, it is not possible to disregard the growing role and importance of biosurfactants in environmental sustainability.Biosurfactant formulations which can be used for bacterial, fungal, and viral organisms as growth inhibitors. Such biosurfactant inhibition properties can make them components that are applicable to Numerous illnesses that are used as medicinal agents. Therefore it was decided that the described strain could be used as a potential source for heavy metal bioremediation pesticide and hydrocarbon polluted sites. And also used as shielding the plant from different pathogens, contributing to improved crop yields. There is no doubt that the biosurfactants are a multifunctional, advanced, versatile, long-lasting and updated type not only for the twenty-first century but beyond. Conflict of interest The authors declared that they have no conflict of interest and the paper presents their own work which does not been infringe any third-party rights, especially authorship of any part of the article is an original contribution, not published before and not being under consideration for publication elsewhere. References Ali, S.R.; Chowdhury, B.R.; Mondal, P. and Rajak, S. “Screening and characterization of biosurfactants producing microorganism from natural environment (Whey spilled soil)”. Nat. Sci. Res. 2013, 3(13), 34–64. Anandaraj, B. and Thivakaran, P. “Isolation and production of biosurfactants producing organism from oil spilled soil”. Biosci. Tech. 2010, 1(3), 120–126. Banat, I.M.; Makkar, R.S. AND Cameotra, S.S. “Potential commercial Application of Microbial Surfactants”. Applied MicrobialBioethanol. 2000, 53, 495-508. Cooper, D. G, Zajic, J. E. and Denis, C. J. Am. Oil Chem. Soc. 1981, 58, 7780. Deleu, M. and Paquot, M. “From Renewable Vegetables Resources to Microorganisms: New Trends in Surfactants”C.R. 2004, 7, 641-646. Eric, Deziel.; Gilles,Pauette.; Richars, Villemur.; Francois,Lepine.; and Jean-Guy, Bisaillon. “Biosurfactants Production by a Soil Pseudomonas Strain Growing on Polycyclic Aromatic Hydrocarbons”. Applied and Environmental Microbiology. 1996, 62(6), 1908-1912. Ghayyomi, J.M.; Forghani, F.; Deog, Hwan, Oh. “Biosurfactant production by Bacillus sp. Isolated from petroleum contaminated soil of Sirri Island”. Ame. J. Appl. Sci, 2012, 9(1), 1-6. Makkar, R.; & Cameotra, S. An update on the use of unconventional substrates for biosurfactant production and their new applications. Applied microbiology and biotechnology. 2002, 58(4), 428-434. Mishra, S.; Jyot, J.; Kuhad, R. C.; & Lal, B. Evaluation of inoculum addition to stimulate in situ bioremediation of oily-sludge-contaminated soil. Environ. Microbiol. 2001, 67(4), 1675-1681. Patil, T. D.; Pawar, S.; Kamble P. N. & Thakare, S. V. “Bioremediation of complex hydrocarbons using microbial consortium isolated from diesel oil polluted soil”. Der ChemicaSinica Journal of Biotechnology. 2012, 3(4), 953-958. Plaza, G.; Zjawiony, I.; and Banat, I. “Use of different methods for detection of thermophilic biosurfactants producing bacteria from hydrocarbon contaminated bioremediation soils”. Petro. Sci. Eng. 2006, 50(1), 71–77. Priya, T.; Usharani, G. “Comparative study for bio-surfactant production by using Bacilus subtilis and Pseudomonas aeruginosa”. Res. Int. 2009, 2(4), 284–287. Rahman, K.S.M.; T.J. Rahman.; S, McClean.; R, Marchant.; and I, M. Banat. “Rhamnolipid biosurfactants production by strains of pseudomonas aeruginosa using low-cost raw materials”. 2002, 18, 1277-1281. H.; Jamshidi, E.;Mazaheri, Assadi. M.; and Bonakdarpour, B. “Isolation and production of bio-surfactant from Pseudomonas aeruginosa isolated from Iranian southers wells oils”. Int. Environ. Sci. Tech. 2005, 2(2), 121–127 Satpute, S.K.; Bhawsar, B.D.; Dhakephalkar, P.K.; and Chopade, B.A. “Assessment of different screening methods for selecting bio-surfactant producing marine bacteria”. Indian J. Marine Sci. 2008, 37, 243–250. Shafeeq, M.; Kokub, D.; Khalid, Z. M.; Khan, A. M.; Malik, K. A. (1989). MIRCEN J. Appl. Microbiol. Biotech. 1989, 5, 505–510. Siegmund, I. and Wagner, F. “New method for detecting rhamnolipids excreted by Pseudomonas species during growth on mineral agar”. Tech. 1991, 5, 265–268. Van Dyke, M. I.; Couture, P.; Brauer, M.; Lee, H. and Trevors, J. T. "Pseudomonas aeruginosa UG2 rhamnolipid biosurfactants structural characterization and their use in removing hydrophobic compounds from soil". J. Microbiol. 1993, 39, 1071-1078. Yin, H.; J, Qiang.; Y, Jia.; J, Ye.; H,Peng.; H, Qin.; N, Zhang. B. “Characteristics of bio-surfactant produced by Pseudomonas aeruginosa S6 isolated from oil containing water”. Process Biochemistry. 2008, 44: 302–308. Youssef, H.; Duncan, El.; Nagle, P.; Savage, N.; Knapp, M.; McInerney, J. “Comparison of methods to detect biosurfactant production by diverse microorganisms”. Microbiol Methods. 2004, 56, 339-347.

Abstract The effect of pre-oxidation on the corrosion behavior of pure Ti covered with a solid NaCl deposit in the humid O2 flow at 600 °C is studied. The oxide scale, formed by pre-oxidation, protects the substrate from the NaCl induced corrosion during the initial stage. However, the corrosion of the pre-oxidized sample is severely accelerated by solid NaCl after an incubation period. The chlorine, generated from the decomposition of solid NaCl, diffuses into the oxide/substrate interface as ions during the incubation period, which was observed by ToF–SIMS. The chlorine at the oxide/substrate interface induces the fast corrosion after the incubation period although the pre-oxidation scale is complete and compact.