Chemical characterization, nano-particle mineralogy and particle size distribution of basalt dust wastes.

Understanding the geochemistry of basalt alteration is central to the study of agriculture systems. Various nano-minerals play an important role in the mobilization of contaminants and their subsequent uptake by plants. We present a new analytical experimental approach in combination with an integrated analytical protocol designed to study basalt alteration processes. Recently, throughout the world, ultra-fine and nano-particles derived from basalt dust wastes (BDW) during "stonemeal" soil fertilizer application have been of great concern for their possible adverse effects on human health and environmental pollution. Samples of BDW utilized were obtained from companies in the Nova Prata mining district in southern Brazil for chemical characterization and nano-mineralogy investigation, using an integrated application of advanced characterization techniques such as X-ray diffraction (XRD), High Resolution-Transmission Electron microscopy (HR-TEM)/Energy Dispersive Spectroscopy (EDS)/(selected-area diffraction pattern) SAED, Field Emission-Scanning Electron Microscopy (FE-SEM/EDS), and granulometric distribution analysis. The investigation has revealed that BDW materials are dominated by SiO2, Al2O3, and Fe2O3, with a complex micromineralogy including alkali feldspar, augite, barite, labradorite, hematite, heulandrite, gypsum, kaolinite, quartz, and smectite. In addition, we have identified a number of trace metals such as Cd, Cu, Cr, and Zn, that are preferentially concentrated into the finer, inhalable, dust fraction and, thus, could present a health hazard in the urban areas around the basalt mining zone. The implication of this observation is that use of these nanometric-sized particulates as soil fertilizer may present different health challenges to those of conventional fertilizers, inviting future work regarding the relative toxicities of these materials. Our investigation on the particle size distribution, nano-particle mineralogy and chemical composition in typical BDW samples highlights the need to develop cleaning procedures to minimize exposure to these natural fertilizing basalt dust wastes and is, thus, of direct relevance to both the industrial sector of basalt mining and to agriculture in the region.

The properties of the nano-minerals and hazardous elements: Potential environmental impacts of Brazilian coal waste fire.

Brazilian coal area (South Brazil) impacted the environment by means of a large number of coal waste piles emplaced over the old mine sites and the adjacent areas of the Criciúma, Urussanga, and Siderópolis cities. The area studied here was abandoned and after almost 30 years (smokeless visual) some companies use the actual minerals derived from burning coal cleaning rejects (BCCRs) complied in the mentioned area for industry tiles or refractory bricks. Mineralogical and geochemical similarities between the BCCRs and non-anthropogenic geological environments are outlined here. Although no visible flames were observed, this study revealed that auto-combustion existed in the studied area for many years. The presence of amorphous phases, mullite, hematite and other Fe-minerals formed by high temperature was found. There is also pyrite, Fe-sulphates (eg. jarosite) and unburnt coal present, which are useful for comparison purposes. Bad disposal of coal-dump wastes represents significant environmental concerns due to their potential influence on atmosphere, river sediments, soils and as well as on the surface and groundwater in the surroundings of these areas. The present study using advanced analytical techniques were performed to provide an improved understanding of the complex processes related with sulphide-rich coal waste oxidation, spontaneous combustion and mineral formation. It is reporting huge numbers of rare minerals with alunite, montmorillonite, szomolnokite, halotrichite, coquimbite and copiapite at the BCCRs. The data showed the presence of abundant amorphous Si-Al-Fe-Ti as (oxy-)hydroxides and Fe-hydro/oxides with goethite and hematite with various degrees of crystallinity, containing hazardous elements, such as Cu, Cr, Hf, Hg, Mo, Ni, Se, Pb, Th, U, Zr, and others. By Principal Component Analysis (PCA), the mineralogical composition was related with the range of elemental concentration of each sample. Most of the nano-minerals and ultra-fine particles found in the burned coal-dump wastes are the same as those commonly associated with coal cleaning rejects, in which oxidation of sulphides plays an important role to environment and human health.

Nano-mineralogy of suspended sediment during the beginning of coal rejects spill.

Ultrafine and nanometric sediment inputs into river systems can be a major source of nutrients and hazardous elements and have a strong impact on water quality and ecosystem functions of rivers and lakes regions. However, little is known to date about the spatial distribution of sediment sources in most large scale river basins in South America. The objective of this work was to study the coal cleaning rejects (CCRs) spill that occurred from a CCRs impoundment pond into the Tubarão River, South Brazil, provided a unique occasion to study the importance and role of incidental nanoparticles associated with pollutant dispersal from a large-scale, acute aquatic pollution event. Multifaceted geochemical research by X-ray diffraction (XRD), High Resolution-Transmission Electron microscopy (HR-TEM)/(Energy Dispersive Spectroscopy) EDS/(selected-area diffraction pattern) SAED, Field Emission-Scanning Electron Microscopy (FE-SEM)/EDS, and Raman spectroscopy, provided an in-depth understanding of importance of a nano-mineralogy approach of Aqueous Pollution Scenarios. The electron beam studies showed the presence of a number of potentially hazardous elements (PHEs) in nanoparticles (amorphous and minerals). Some of the neoformed ultrafine/nanoparticles found in the contaminated sediments are the same as those commonly associated with oxidation/transformation of oxides, silicates, sulfides, and sulfates. These data of the secondary ultra/nanoparticles, puts in evidence their ability to control the mobility of PHEs, suggesting possible presentations in environmental technology, including recuperation of sensitive coal mine. The developed methodology facilitated the sediment transport of the catchment providing consistent results and suggesting its usefulness as a tool for temporary rivers management.

Modification, adsorption, and geochemistry processes on altered minerals and amorphous phases on the nanometer scale: examples from copper mining refuse, Touro, Spain.

The sulfide oxidation and precipitation of Al-Fe-secondary minerals associated with abandoned acid mine drainage (AMD) from the abandoned copper mine waste pile at Touro, Spain, has been studied by sequential extraction (SE) combined with several techniques with the intent of understanding the role of these processes play in the natural attenuation of hazardous element contaminants in the AMD. In addition, the fragile nature of nanominerals and ultrafine particle (UFP) assemblages from contaminated sediment systems from the abandoned copper mine required novel techniques and experimental approaches. The investigation of the geochemistry of complex nanominerals and UFP assemblages was a prerequisite to accurately assess the environmental and human health risks of contaminants and cost-effective chemical and biogeological remediation strategies. Particular emphasis was placed on the study and characterization of the complex mixed nanominerals and UFP containing potentially toxic elements. Nanometer-sized phases in sediments were characterized using energy-dispersive X-ray spectrometer (EDS), field-emission scanning electron microscope (FE-SEM), and high-resolution transmission electron microscopy (HR-TEM) images. The identification of the geochemical and mineralogical composition of AMD in Touro, as well as the different formation mechanisms proposed, complement the existing literature on secondary mineral assemblages and provide new emphasis to increase the understanding of extreme environments. The results also demonstrated that variations in the geochemical fractionation of hazardous elements in AMD were more influenced by the secondary mineral proportion and by AMD pH.

Potential utilization for the evaluation of particulate and gaseous pollutants at an urban site near a major highway.

Works of particle number and mass concentration variability have a great importance since they may indicate better the influence of vehicle emissions in an urban region. Moreover, the importance of this work lies in the fact that there are few studies in Brazil, where the fuel used has unique characteristics. Consequently, this paper presents measurements of particle number (size range 0.3-10 µm), particle mass (PM10, PM2.5, PM1), O3 and NOx (NO, NO2), in a site near a major highway at the Metropolitan Area of Porto Alegre, south Brazil. Measurements were carried out during two years: 2012 and 2013. Particle number and mass concentrations were measured using an optical counter with a PM10 analyzer. Results showed that concentrations of N0.3-1 (0.3-1 µm) were the highest, although similar to N1-2.5 (1-2.5 µm). Daily variability of the analyzed pollutants followed the traffic pattern. Moreover, NO2, O3, and particle number were higher during the day, whereas NO, NOx, and particle matter showed higher concentrations during nighttime. Traffic influence was evidenced by the mean concentrations of weekends and weekdays, being higher for the latter. Correlation of particles and gases with meteorological variables, together with the application of PCA confirmed the influence of vehicle exhaust discharges.

Nanoparticulate mineral matter from basalt dust wastes.

Ultra-fine and nano-particles derived from basalt dust wastes (BDW) during "stonemeal" soil fertilizer application have been the subject of some concern recently around the world for their possible adverse effects on human health and environmental pollution. Samples of BDW utilized were obtained from companies in the mining district of Nova Prata in southern Brazil for chemical characterization and nano-mineralogy investigation, using an integrated application of advanced characterization techniques such as X-ray diffraction (XRD), High Resolution-Transmission Electron microscopy (HR-TEM)/(Energy Dispersive Spectroscopy) EDS/(selected-area diffraction pattern) SAED, Field Emission-Scanning Electron Microscopy (FE-SEM)/EDS and granulometric distribution analysis. The investigation has revealed that BDW materials are dominated by SiO2, Al2O3 and Fe2O3, with a complex micromineralogy including alkali feldspar, augite, barite, labradorite, hematite, heulandrite, gypsum, kaolinite, quartz, and smectite. In addition we have identified a number of trace metals such as Cd, Cu, Cr, Zn that are preferentially concentrated into the finer, inhalable, dust fraction and could so present a health hazard in the urban areas around the basalt mining zone. The implication of this observation is that use of these nanometric-sized particulates as soil fertilizer may present different health challenges to those of conventional fertilizers, inviting future work regarding the relative toxicities of these materials. Our investigation on the particle size distribution, nano-particle mineralogy and chemical composition in typical BDW samples highlights the need to develop cleaning procedures to minimise exposure to these natural fertilizing basalt dust wastes and is thus of direct relevance to both the industrial sector of basalt mining and to agriculture in the region.

A preliminary evaluation of volcanic rock powder for application in agriculture as soil a remineralizer.

Mineralogical and geochemical characteristics of volcanic rock residue, from a crushing plant in the Nova Prata Mining District, State of Rio Grande do Sul (RS), Brazil, in this work named rock powder, were investigated in view of its potential application as soil ammendment in agriculture. Abaut 52,400 m(3) of mining waste is generated annually in the city of Nova Prata without a proper disposal. The nutrients potentially available to plants were evaluated through leaching laboratory tests. Nutrient leaching tests were performed in Milli-Q water; citric acid solution 1% and 2% (AC); and oxalic acid solution 1% and 5% (AO). The bulk and leachable contents of 57 elements were determined by inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES). Mining waste were made up by CaO, K2O, SiO2, Al2O3, Fe2O3, and P2O5. The analysis by X-ray diffraction (XRD) showed the major occurence of quartz, anorthite, cristobalite, sanidine, and augite. The water leachable concentrations of all elements studied were lower than 1.0mg/kg, indicating their low solubility. Leaching tests in acidic media yield larger leachable fractions for all elements being studied are in the leachate of the AO 1%. These date usefulness of volcanic rock powder as potential natural fertilizer in agriculture in the mining district in Nova Prata, Rio Grande do Sul, Brazil to reduce the use of chemical fertilizers.

Fate of hazardous elements in agricultural soils surrounding a coal power plant complex from Santa Catarina (Brazil).

Hazard element contamination coming from coal power plants is something obvious, but when this contamination is accompanied by other contamination sources, such as, urban, coal mining and farming activities the study gets complicated. This is the case of an area comprised in the southern part of Santa Catarina state (Brazil) with the largest private power plant generator. After the elemental analysis of 41 agricultural soils collected in an extensive area around the thermoelectric (from 0 to 47 km), the high presence of As, Co, Cr, Cu, Fe, Mn, Mo, Pb, Sb, Sn, Tl, V and Zn was found in some specific areas around the power plant. Nevertheless, as the NWAC (Normalized-and-Weighted Average Concentration) confirmed, only soils from one site were classified as of very high concern due to the presence of potential toxic elements. This site was located within the sedimentation basin of the power plant. The spatial distribution obtained by kriging in combination with the analysis of the data by Principal Component Analysis (PCA) revealed three important hotspots in the area according to soil uses and geographic localization: the thermoelectric, its area of influence due to volatile compound deposition, and the area comprised between two urban areas. Farming practice turn out to be an important factor too for the quantity of hazard element stored in soils.

Direct identification of hazardous elements in ultra-fine and nanominerals from coal fly ash produced during diesel co-firing.

This study has provided an initial assessment of the environmental impacts and potential health effects associated with coal fly ash produced during diesel co-firing. Many hazardous elements that are typically detected by multifaceted chemical characterization by XRD, petrology, FE-SEM/EDS, and HR-TEM/SEAD/FFT/EDS in ultra-fine compounds and nanominerals from the co-fired coal fly ashes (CFAs). It provided an in-depth understanding of coal ash produced during diesel co-firing. Several of the neoformed ultra-fine compounds and nano-minerals found in the coal ashes are the same as those commonly associated with oxidation/transformation of aluminosilicates, carbonates, sulphides and phosphates.