Acid mine drainage formation and arsenic mobility under strongly acidic conditions: Importance of soluble phases, iron oxyhydroxides/oxides and nature of oxidation layer on pyrite.

Acid mine drainage (AMD) formation and toxic arsenic (As) pollution are serious environmental problems encountered worldwide. In this study, we investigated the crucial roles played by common secondary mineral phases formed during the natural weathering of pyrite-bearing wastes-soluble salts (melanterite, FeSO4·7H2O) and metal oxides (hematite, Fe2O3)-on AMD formation and As mobility under acidic conditions (pH 1.5-4) prevalent in historic tailings storage facilities, pyrite-bearing rock dumps and AMD-contaminated soils and sediments. Our results using a pyrite-rich natural geological material containing arsenopyrite (FeAsS) showed that melanterite and hematite both directly-by supplying H+ and/or oxidants (Fe3+)-and indirectly-via changes in the nature of oxidation layer formed on pyrite-influenced pyrite oxidation dynamics. Based on SEM-EDS, DRIFT spectroscopy and XPS results, the oxidation layer on pyrite was mainly composed of ferric arsenate and K-Jarosite when melanterite was abundant with/without hematite but changed to Fe-oxyhydroxide/oxide and scorodite when melanterite was low and hematite was present. This study also observed the formation of a mechanically 'strong' coating on pyrite that suppressed the mineral's oxidation. Finally, As mobility under acidic conditions was limited by its precipitation as ferric arsenate, scorodite, or a Fe/Al arsenate phase, including its strong adsorption to Fe-oxyhydroxides/oxides.

Improved pyrolysis behavior of ammonium polyphosphate-melamine-expandable (APP-MEL-EG) intumescent fire retardant coating system using ceria and dolomite as additives for I-beam steel application.

This study describes the effects of ceria (CeO2) and dolomite [CaMg(CO3)2] additives on the pyrolysis behavior and fire resistive property of conventional intumescent flame retardant (IFR) coating system for I-beam steel substrate called ammonium polyphosphate-melamine-expandable graphite (APP-MEL-EG) system. The fire resistance of various formulations was evaluated using the standard vertical Bunsen burner fire test. Thermogravimetric analysis (TGA) was used to understand the degradation of coating formulations. Observations by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX) demonstrated that significant amounts of additives favored the formation of homogeneous compacted char structures, which were predominantly composed of carbon (C), phosphorus (P) and oxygen (O). These three main components of the char were also found to be in various binding combinations with other lighter elements like nitrogen (N) and hydrogen (H) as illustrated by the attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy results. X-ray photoelectron spectroscopy (XPS) further suggest that polyethylene([(CH2-C2H2-CH2)n-]) free radicals were abundant on the char surface for the two best formulations and the binding energy of this radical promoted the formation of aromatic carbon chains that enhanced the char's thermal stability. This means that the selection of appropriate additives and combinations of flame-retardant ingredients could significantly change the morphology of the char layer and improve its thermal stability during fire exposure.

Hematite-catalysed scorodite formation as a novel arsenic immobilisation strategy under ambient conditions.

Scorodite is an important mineral not only for arsenic (As) removal from industrial wastewaters but also in the mobility and final fate of As in waste rocks, contaminated soils and sediments, and mine tailings. Because of the mineral's high As-loading capacity and stability, numerous studies have been done to understand its formation. Unfortunately, most of these studies were limited to elevated temperatures (>70 °C), so the processes involved in scorodite formation under ambient conditions remain unclear. This study provides evidence of the catalytic effects of hematite on the formation of scorodite at 25 °C in a pyrite-rich natural geologic material. Scorodite peaks were detected in the XRD patterns of the leaching residues with and without hematite, but those in the former were stronger and more pronounced than the latter. These results suggest that the formation of scorodite was catalysed by hematite, a generalisation that is further supported by strong characteristic IR absorption bands of scorodite at 819 cm-1 (As-O bending vibration), 785 and 725 cm-1 (As-O stretching vibrations), and 2990 cm-1 (OH-vibration) as well as the distinct XPS binding energies of Fe(III)-As (709.7 eV), As(V)-O (44.8, 44.31 and 43.7 eV), O2- (530.5 eV) and coordinated water (531.3 eV) in scorodite. This phenomenon could be attributed to three possible mechanisms: (1) more rapid precipitation promoted by the "seeding" effect of hematite particles, (2) additional supply of Fe3+ from hematite dissolution under acidic conditions, and (3) enhanced oxidations of Fe2+ to Fe3+ and As(III) to As(V) on the surface of hematite.

Matrix Sputtering Method: A Novel Physical Approach for Photoluminescent Noble Metal Nanoclusters.

Noble metal nanoclusters are believed to be the transition between single metal atoms, which show distinct optical properties, and metal nanoparticles, which show characteristic plasmon absorbance. The interesting properties of these materials emerge when the particle size is well below 2 nm, such as photoluminescence, which has potential application particularly in biomedical fields. These photoluminescent ultrasmall nanoclusters are typically produced by chemical reduction, which limits their practical application because of the inherent toxicity of the reagents used in this method. Thus, alternative strategies are sought, particularly in terms of physical approaches, which are known as "greener alternatives," to produce high-purity materials at high yields. Thus, a new approach using the sputtering technique was developed. This method was initially used to produce thin films using solid substrates; now it can be applied even with liquid substrates such as ionic liquids or polyethylene glycol as long as these liquids have a low vapor pressure. This revolutionary development has opened up new areas of research, particularly for the synthesis of colloidal nanoparticles with dimensions below 10 nm. We are among the first to apply the sputtering technique to the physical synthesis of photoluminescent noble metal nanoclusters. Although typical sputtering systems have relied on the effect of surface composition and viscosity of the liquid matrix on controlling particle diameters, which only resulted in diameters ca. 3-10 nm, that were all plasmonic, our new approach introduced thiol molecules as stabilizers inspired from chemical methods. In the chemical syntheses of metal nanoparticles, controlling the concentration ratio between metal ions and stabilizing reagents is a possible means of systematic size control. However, it was not clear whether this would be applicable in a sputtering system. Our latest results showed that we were able to generically produce a variety of photoluminescent monometallic nanoclusters of Au, Ag, and Cu, all of which showed stable emission in both solution and solid form via our matrix sputtering method with the induction of cationic-, neutral-, and anionic-charged thiol ligands. We also succeeded in synthesizing photoluminescent bimetallic Au-Ag nanoclusters that showed tunable emission within the UV-NIR region by controlling the composition of the atomic ratio by a double-target sputtering technique. Most importantly, we have revealed the formation mechanism of these unique photoluminescent nanoclusters by sputtering, which had relatively larger diameters (ca. 1-3 nm) as determined using TEM and stronger emission quantum yield (max. 16.1%) as compared to typical photoluminescent nanoclusters prepared by chemical means. We believe the high tunability of sputtering systems presented here has significant advantages for creating novel photoluminescent nanoclusters as a complementary strategy to common chemical methods. This Account highlights our journey toward understanding the photophysical properties and formation mechanism of photoluminescent noble metal nanoclusters via the sputtering method, a novel strategy that will contribute widely to the body of scientific knowledge of metal nanoparticles and nanoclusters.

Synthesis of Positively Charged Photoluminescent Bimetallic Au-Ag Nanoclusters by Double-Target Sputtering Method on a Biocompatible Polymer Matrix.

Herein, we report a novel positively charged photoluminescent Au-Ag bimetallic nanocluster synthesized using 11-mercaptoundecyl-N,N,N-trimethylammonium bromide as the capping ligand by means of "green" double-target sputtering method on a biocompatible polymer matrix. The photoluminescent Au-Ag bimetallic cluster showed emission tunability from blue to near infrared (NIR) regions with respect to change in the composition.

Controlling an electrostatic repulsion by oppositely charged surfactants towards positively charged fluorescent gold nanoclusters.

A novel positively charged fluorescent gold nanocluster was successfully synthesized using the shortest cationic thiol, thiocholine. Effective control of electrostatic repulsion by the introduction of an anionic surfactant afforded a nanocluster that showed blue fluorescence emission.