In the current study, different heavy minerals typical of gold placer deposits were identified by means of micro-Raman spectroscopy, and their chemical composition analyzed and discussed (garnet, kyanite, staurolite, zircon, allanite, monazite, xenotime, rutile, anatase, cassiterite, titanite, barite). Even complex solid solution series, such as those of garnets, can be deciphered with the aid of systematic trends observed in Raman line frequencies. The ν1 mode in garnets will shift from high to low frequencies as a function of the ionic radius of the X2+ cation, from Mg2+, to Fe2+ and Mn2+, while the presence of Ca2+ will make the band to be shifted strongly to even lower wavenumbers. This approach has successfully been taken to differentiate between polymorph triplets such as kyanite-sillimanite-andalusite and rutile-anatase-brookite. Minerals under consideration with high contents of REE, U and Th are affected by intensive metamictization, particularly zircon and titanite. Raman peak features, such as shape, symmetry and intensity, respond to this radiation damage of the lattice and enable fine-tuning of these heavy minerals, such as in the case of fluorite (fetid fluorite).
Two environmentally friendly organics (ethylenediaminetetraacetic acid, EDTA and its easier biodegradabe isomer, ethylenediamine-N, N′-disuccinic acid, EDDS) were used to dope calcium carbonate (CC) nanoparticles intending to increase their adsorptive properties and evaluate adsorption performance (uptake capacity and removal efficiency) for the persistent Reactive Yellow 84 azo dye. Easily synthesized nanomaterials were fully characterized (morphology and size, mineralogy, organic content, surface area, pore size and hydrodynamic diameter). RY84 removal was performed using two consecutive processes: photodegradation after adsorption. The CC-EDTA particles were most efficient for dye removal as compared to the plain and CC-EDDS particles. Adsorption kinetics and isotherms were considered for the CC-EDTA system. 99% removal occurred via adsorption on 1 g/L of adsorbent at 5 mg/L dye concentration and pH of 8 and it decreased to 48% at 60 mg/L. Maximum uptake capacity as described by Langmuir is 39.53 mg/g. As post-adsorption, under UVA irradiation, in the presence of 40 mmol/L H2O2, at dye concentration of 10 mg/L the highest degradation was 49.11%. Substantial decrease of adsorption (ca. 4 times) and photodegradation (ca. 5 times) efficiencies were observed in wastewater effluent as compared to distilled water. The results have important implications to wastewater treatments and appropriate decisions making for the choice of treatment process, process optimization and scaling up to pilot and industrial levels.
Sphalerite is an abundant mineral in the hydrothermal deposits from the Baia Mare and Oaș areas (northwestern Romania). Sphalerite samples were analyzed with an electron probe microanalyzer and Raman spectroscopy. The obtained results indicated different amounts of Fe in the various deposits from the Baia Mare and Oaș areas. The sphalerites from Baia Sprie, Cavnic, Iba, Turț Penigher, and Breiner have a low Fe wt.% content. High Fe wt.% contents are at Herja and partly at Ghezuri and Nistru (copper stage) where sphalerite is associated with pyrrhotite. The correlation between iron and zinc from sphalerites is strongly negative. The negative correlation shows that iron is the main element that replaces zinc in the sphalerite structure. The manganese content of sphalerites in the Baia Mare and Oaș area is up to 0.84 wt.%. The cadmium content is quite uniform in the Baia Mare and Oaș area with contents ranging from 0.01 to 0.72 wt.%. The Fe content of sphalerites is an important indicator of the physico-chemical conditions of deposit formation because it is a function of temperature, pressure, and sulfur fugacity.
Minor elements received more attention in recent years due to their contamination susceptibility and environmental impact. Surface sediment samples were collected from 29 sites and total contents of eight minor elements (Cr, Co, Ni, Cu, Zn, As, Cd, and Pb) were investigated in order to determine the geostatistical distribution and to predict ecological implications. The relationship between metals and ecological implications was analyzed by using the geochemical normalization approach and ecological prediction indicators such as the enrichment factor (EF), the contamination degree (CD), the environmental toxicity quotient (ETQ), and the health risk assessment. Based on the studied toxic metals, it was observed that the most toxic element in Tazlău River sediments is Cr. The assessment results of carcinogenic and non-carcinogenic risks via dermal contact indicate that the study area shows no human health risk. The correlation matrix and principal component analysis (PCA) provide an overview of the major sources, anthropogenic versus geogenic, where Cr and Cd mainly originate from anthropogenic sources, while Pb is derived from a geogenic source. The approaches used in this study will provide a baseline regarding the accumulation of minor elements in the sediment and will be useful for other studies to easily identify the major contaminates and to estimate the health human risk.
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