Marcos L.S. Oliveira

Chemical composition and minerals in pyrite ash of an abandoned sulphuric acid production plant.

The extraction of sulphur produces a hematite-rich waste, known as roasted pyrite ash, which contains significant amounts of environmentally sensitive elements in variable concentrations and modes of occurrence. Whilst the mineralogy of roasted pyrite ash associated with iron or copper mining has been studied, as this is the main source of sulphur worldwide, the mineralogy, and more importantly, the characterization of submicron, ultrafine and nanoparticles, in coal-derived roasted pyrite ash remain to be resolved. In this work we provide essential data on the chemical composition and nanomineralogical assemblage of roasted pyrite ash. XRD, HR-TEM and FE-SEM were used to identify a large variety of minerals of anthropogenic origin. These phases result from highly complex chemical reactions occurring during the processing of coal pyrite of southern Brazil for sulphur extraction and further manufacture of sulphuric acid. Iron-rich submicron, ultrafine and nanoparticles within the ash may contain high proportions of toxic elements such as As, Se, U, among others. A number of elements, such as As, Cr, Cu, Co, La, Mn, Ni, Pb, Sb, Se, Sr, Ti, Zn, and Zr, were found to be present in individual nanoparticles and submicron, ultrafine and nanominerals (e.g. oxides, sulphates, clays) in concentrations of up to 5%. The study of nanominerals in roasted pyrite ash from coal rejects is important to develop an understanding on the nature of this by-product, and to assess the interaction between emitted nanominerals, ultra-fine particles, and atmospheric gases, rain or body fluids, and thus to evaluate the environmental and health impacts of pyrite ash materials.

Evaluation of soil gram-negative bacteria yielding polyhydroxyalkanoic acids from carbohydrates and propionic acid

Abstract A screening programme was developed leading to the isolation of 75 strains of soil gram-negative bacteria which are able to produce polyhydroxyalkanoic acids (PHA) from sugar-cane derivatives. The evaluation of these strains was performed with regard to their efficiency in converting carbohydrates or propionic acid into PHA constituents. Several strains were able to use sucrose as well as glucose and fructose to grow and afterwards to accumulate poly-(3-hydroxybutyric acid) (PHB) with promising yields. Seven strains were found to have more than 80% of the theoretical value when converting carbohydrates into PHB and accumulated at least 50% of the cell dry weight as PHB. Ten strains incorporated 3-hydroxyvaleric acid units into the polymer from propionic acid of which 3 gave yields comparable to those of Alcaligenes eutrophus.

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.

Leaching of potential hazardous elements of coal cleaning rejects

The geochemical characteristics of coal cleaning rejects (CCR) in Santa Catarina State, Brazil, were investigated. Around 3.5 million ton/ year of coal waste are dumped in Santa Catarina State. Coal beneficiation by froth flotation results in large amounts of CCR composed of coaly and mineral matter, the latter characterised by the occurrence of sulphide minerals and a broad array of leachable elements. The total and leachable contents of more than 60 elements were analysed. Atmospheric exposure promotes sulphide oxidation that releases substantial sulphate loads as well as Ca2 + , K + , Mg2 + , Cl −  and Al3 + . The metals with the most severe discharges were Zn, Cu, Mn, Co, Ni and Cd. Most trace pollutants in the CCR displayed a marked pH-dependent solubility, being immobile in near-neutral samples. The results highlight the complex interactions among mineral matter solubility, pH and the leaching of potentially hazardous elements.

Study of environmental pollution and mineralogical characterization of sediment rivers from Brazilian coal mining acid drainage

Acid drainage from coal mines and metal mining is a major source of underground and surface water contamination in the world. The coal mining acid drainage (CMAD) from mine contains large amount of solids in suspension and a high content of sulphate and dissolved metals (Al, Mn, Zn, Cu, Pb, Fe, etc.) that finally are deposited in the rivers. Since this problem can persist for centuries after mine abandonment, it is necessary to apply multidisciplinary methods to determine the potential risk in a determinate area. These multidisciplinary methods must include molecular and elemental analysis and finally all information must be studied statistically. This methodology was used in the case of coal mining acid drainage from the Tubarao River (Santa Catarina, Brazil). During molecular analysis, Raman Spectroscopy, electron bean, and X-ray diffraction (XRD) have been proven very useful for the study of minerals present in sediment rivers near this CMAD. The obtained spectra allow the precise identification of the minerals as jarosite, quartz, clays, etc. The elemental analysis (Al, As, Fe, K, Na, Ba, Mg, Mn, Ti, V, Zn, Ag, Co, Li, Mo, Ni, Se, Sn, W, B, Cr, Cu, Pb and Sr) was realised by inductively coupled plasma mass spectrometry (ICP-MS). Statistical analysis (Principal Component Analysis) of these dates of concentration reveals the existence of different groups of samples with specific pollution profiles in different areas of the Tubarao River.

A preliminary study of coal mining drainage and environmental health in the Santa Catarina region, Brazil.

The concentrations and loadings of major and trace elements in coal mine drainage (CMD) from 49 abandoned mines located in the coal fields of the Brazilian state of Santa Catarina were determined. The CMD sites typically displayed a wide spatial and temporal variability in physical and geochemical conditions. The results of our CMD analyses in Santa Catarina State were used to illustrate that the geochemical processes in the rock piles can be deduced from multiple data sets. The observed relationship between the pH and constituent concentrations were attributed to (1) dilution of acidic water by near-neutral or alkaline groundwater and (2) solubility control of Al, Fe, Mn, Ba and Sr by hydroxide, sulfate, and/or carbonate minerals. The preliminary results of the CMD analyses and environmental health in the Santa Catarina region, Brazil, are discussed.

Geochemistry of ultra-fine and nano-compounds in coal gasification ashes: A synoptic view

The nano-mineralogy, petrology, and chemistry of coal gasification products have not been studied as extensively as the products of the more widely used pulverized-coal combustion. The solid residues from the gasification of a low- to medium-sulfur, inertinite-rich, volatile A bituminous coal, and a high sulfur, vitrinite-rich, volatile C bituminous coal were investigated. Multifaceted chemical characterization by XRD, Raman spectroscopy, petrology, FE-SEM/EDS, and HR-TEM/SEAD/FFT/EDS provided an in-depth understanding of coal gasification ash-forming processes. The petrology of the residues generally reflected the rank and maceral composition of the feed coals, with the higher rank, high-inertinite coal having anisotropic carbons and inertinite in the residue, and the lower rank coal-derived residue containing isotropic carbons. The feed coal chemistry determines the mineralogy of the non-glass, non-carbon portions of the residues, with the proportions of CaCO₃ versus Al₂O₃ determining the tendency towards the neoformation of anorthite versus mullite, respectively. Electron beam studies showed the presence of a number of potentially hazardous elements in nanoparticles. Some of the neoformed ultra-fine/nano-minerals found in the coal ashes are the same as those commonly associated with oxidation/transformation of sulfides and sulfates.

Coal cleaning residues and Fe-minerals implications

In the present investigation, a study was undertaken to understand the origin of Fe-minerals presents in Brazilian coal mining and to understand the environmental implication and the chemical heterogeneity in the study area. Coal cleaning residue samples rich in clays, quartz, sulphides, carbonates, sulphates, etc. were sampled from Lauro Muller, Urussanga, Treviso, Siderópolis, and Criciúma cities in the Santa Catarina State and a total of 19 samples were collected and Mössbauer, XRD, SEM/EDX, and TEM analyses were conducted on the samples. The major Fe-minerals identified are represented by the major minerals chlorite, hematite, illite, and pyrite, while the minor minerals include, ankerite, chalcopyrite, goethite, hematite, jarosite, maghemite, magnetie, marcasite, melanterite, natrojarosite, oligonite, pyrrhotite, rozenite, schwertmannite, siderite, and sideronatrile. Pyrite is relatively abundant in some cases, making up to around 10% of the mineral matter in several samples. The sulphates minerals such as jarosite and others, probably represent oxidation products of pyrite, developed during exposure or storage.

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.

Nano-mineralogical investigation of coal and fly ashes from coal-based captive power plant (India): an introduction of occupational health hazards.

Coal derived nano-particles has been received much concern recently around the world for their adverse effects on human health and the environment during their utilization. In this investigation the mineral matter present in some industrially important Indian coals and their ash samples are addressed. Coal and fly ash samples from the coal-based captive power plant in Meghalaya (India) were collected for different characterization and nano-mineralogy studies. 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 analysis, and Mössbauer spectroscopy were used to know their extent of risks to the human health when present in coal and fly ash. The study has revealed that the coals contain mainly clay minerals, whilst glass fragments, spinel, quartz, and other minerals in lesser quantities were found to be present in the coal fly ash. Fly ash carbons were present as chars. Indian coal fly ash also found to contain nanominerals and ultrafine particles. The coal-fired power plants are observed to be the largest anthropogenic source of Hg emitted to the atmosphere and expected to increase its production in near future years. The Multi Walled Carbon Nano-Tubes (MWCNTs) are detected in our fly ashes, which contains residual carbonaceous matter responsible for the Hg capture/encapsulation. This detailed investigation on the inter-relationship between the minerals present in the samples and their ash components will also be useful for fulfilling the clean coal technology principles.