Correlation study of air pollution and cardio-respiratory diseases through NAA of an atmospheric pollutant biomonitor

In this study neutron activation analysis was applied to analyze lichen samples used as atmospheric pollutant biomonitors in order to verify if there is correlation between air pollution and its effects on the cardio respiratory system. Canoparmelia texana lichenized fungii species was chosen for passive biomonitoring of atmospheric pollutants. The population group selected for this study was adults over 45 years. Lichen samples collected in São Paulo city were cleaned, freeze-dried and ground for the analyses. Aliquots of samples were irradiated at the IEA-R1 nuclear research reactor for short and long periods along with synthetic element standards. The induced gamma activities of the samples and standards were measured using a gamma ray spectrometer with an HPGe detector and the concentrations of As, Ba, Br, Ca, Cd, Cl, Co, Cr, Cs, Fe, Hf, K, Mg, Mn, Na, Rb, Sb, Sc, Se,Th, V, Zn and lanthanides were determined. For quality control of the results, certified reference materials were analyzed together. Mortality data for the population due to cardio-respiratory diseases were obtained from the database of the Secretariat of Health of the São Paulo Municipality for the years 2005–2009. Results obtained point to vehicular and industrial emissions as the origins of pollutants in São Paulo city. The statistical treatment of Pearson’s correlation applied to the results of lichen element concentrations and mortality rates indicated significant positive correlation for the elements Co, Mn and Zn for adults.     

Total Diet Study: Mg and Mn content estimation of a Market Basket of São Paulo state (Brazil) by Instrumental Neutron Activation

Total Diet Studies (TDS) have been carried out to estimate dietary intakes of the essential and toxic elements for a large-scale population over a specific period of time. In this study, the TDS was based on the evaluation of food representing a Market Basket (MB), which reflected the dietary habits of the São Paulo State population, corresponding to 72 % of the average food consumption for the state of São Paulo. In the present Total Diet Study, magnesium and manganese concentrations were determined in 30 of the most consumed food groups of a MB of São Paulo State, Brazil. Instrumental Neutron Activation Analysis (INAA) has been successfully used on a regularly basis in several areas of nutrition and foodstuffs. Element concentrations were determined by INAA in freeze-dried samples and ranged in mg kg^?1. Mg 41.4 (fats)–5287 (coffee) and Mn 0.12 (prime grade beef)–32.9 (coffee). The average daily Mg and Mn intake was calculated by multiplying the concentration of each element in each table-ready food group by the respective weight (g day^?1) of the food group in the MB and adding the products from all food groups. The results of daily dietary intakes in this study were: Mg 174.8 and Mn 1.34 mg day^?1. Theses values were lower than the adequate intake (AI) proposed by the Food and Nutrition Board of the Institute of Medicine (USA National Academy) for adults. The low levels of Mg and Mn intakes presented in this TDS are probably due to the fact that MB of this study represented only 72 % of the weight of the most consumed household foods of São Paulo State.     

Metals and semi-metals in street soils of São Paulo city,Brazil

São Paulo is the largest city in Brazil and South America with about 20 million inhabitants in the metropolitan area, more than nine million motor vehicles and intense industrial activity, which are responsible for increasing pollution in the region. Nevertheless, little is known concerning metal and semi-metal content in the soils of this metropolitan region. This type of information could be extremely useful as a fingerprint of environmental pollution. The present study determined the elements As, Ba, Co, Cr, Sb, and Zn concentrations in soils adjacent to avenues of highly dense traffic in São Paulo city to assess their levels and possible sources. The analytical technique employed was Instrumental neutron activation analysis. The results showed, except for Co, concentration levels higher than the reference values for soils of São Paulo, according to the Environmental Protection Agency of the State of São Paulo guidelines. When compared to similar studies in other cities around the world, São Paulo soils presented higher levels, probably due to its high density traffic and industrial activity. The concentrations obtained for As and Cr indicate anthropogenic origin. The high levels of the traffic-related elements Ba, Sb, and Zn in soils nearby high density traffic avenues indicate they may originate from vehicular exhausts.     

Neutron activation analysis applied in sediment samples from the Guarapiranga Reservoir for metals and trace elements assessment

The Guarapiranga Reservoir is a very important aquatic system due to the fact that it is one of the main water reservoirs for South America’s largest city, São Paulo, Brazil. Guarapiranga basin is located within the Metropolitan Region of São Paulo and the reservoir itself is located in the Northern part of the basin occupying approximately 26 km². This reservoir is characterized by environmental impacts from urban invasion, industrial and sewage wastes, all of which seriously affect its water quality and, consequently, the sediment quality. Two collection campaigns were undertaken: April 2009 and June 2010. The samples were analyzed by instrumental neutron activation analysis (INAA) in order to determine the following elements: major (Fe, K and Na), trace (As, Ba, Br, Co, Cr, Cs, Hf, Rb, Sb, Sc, Ta, Tb, Th, U and Zn) and rare earths (Ce, Eu, La, Lu, Nd, Sm, Tb and Yb). The organic matter and granulometric distribution were also evaluated and multivariate analysis was applied to the results. The study of elemental ratios indicated that the amount of elements present in the Guarapiranga Reservoir is mainly of detrital origin.     

Waste and fuels from waste

Thermogravimetric studies provide the basis for qualification of materials and suitability of biomass fuels and fuels formed from waste to convert them into fuel gas generated in the generator process. The paper presents the results of the analysis of thermal decomposition (thermogravimetric research) of fuel from waste, sewage sludge and wastes from the agro-food: potato pulp and rapeseed meal. Studies have shown how some biofuels and fuel formed from waste reach the semi-coke and coke structure, which is important later, in modeling industry degassing process. The most effective seems to be using rapeseed meal in generator process, since the thermal decomposition occurs in the form of transformation in the temperature range 200?C500?°C. On the basis of quantity analysis of gaseous transformation products from the above mentioned transformations, the calorific value of after process gases has been calculated. The highest calorific value is represented by a gas resulting from rapeseed meal pyrolysis ~10,040?kJ/Nm³. The solid residue obtained by dry decomposition of potato pulp has the highest energy value when compared with products from other fuels.     

Thermal analysis of soil amended with sewage sludge and biochar from sewage sludge pyrolysis

The main objective of the present study is to study the behaviour of sewage sludge and biochar from sewage sludge pyrolysis after addition to soil in a context of a temperate agricultural soil. For this, an incubation experiment was designed during 200 days. Carbon mineralization of soil amended with sewage sludge and biochar at two different rates (4 and 8 wt%) was evaluated. Differential thermal analysis, thermogravimetry and the first derivate of the TG were performed in oxidizing conditions on soil samples before and after incubation. Biochar obtained from sewage sludge pyrolysis at 500 °C was more stable in soil than original sewage sludge. After incubation experiment, the reduction of soil organic matter content was significantly lower in soil amended with biochar than in soil amended with sewage sludge. The thermostability index WL₃/WL₂ decreases after incubation in soil amended with biochar, however it increases in case of soil treated with sewage sludge.     

Thermal characteristics of the combustion process of biomass and sewage sludge

The combustion of two kinds of biomass and sewage sludge was studied. The biomass fuels were wood biomass (pellets) and agriculture biomass (oat). The sewage sludge came from waste water treatment plant. The biomass and sludge percentage in blends with coal were 10 %. The studied materials were characterised in terms of their proximate and ultimate analysis and calorific value. The composition of the ash of the studied fuels was also carried out. The behaviour of studied fuels was investigated by thermogravimetric analysis (TG, DTG and DTA). The samples were heated from an ambient temperature up to 1,000 °C at a constant three rates: 10, 40 and 100 °C min^?1 in 40 mL min^?1 air flow. TG, DTG and DTA analysis showed differences between coal, biomass fuels and sewage sludge. 10 % addition of studied fuels to the mixture with coal changed its combustion profile in the case of sewage sludge addition. The combustion characteristics of fuel mixtures showed, respectively, qualitative summarise behaviour based on single fuels. Evolved gaseous products from the decomposition of studied samples were identified. This study showed that thermogravimetric analysis connected with mass spectrometry is useful techniques to investigate the combustion and co-combustion of biomass fuels, and sewage sludge, together with coal. Non-isothermal kinetic analysis was used to evaluate the Arrhenius activation energy and the pre-exponential factor. The kinetic parameters were calculated using Kissinger–Akahira–Sunose model.     

Biomonitoring of the atmospheric pollution using lichens in the metropolitan area of São Paulo city,Brazil

The atmospheric pollution of São Paulo city is a serious problem due to the expansion of industrial area, increasing number of vehicles and population density. This work presents results obtained in the analysis of lichens collected in different sites of São Paulo city and in non-polluted areas of Atlantic Forest. Concentrations of twenty elements were determined in Canoparmelia texana species and comparisons were made between the results obtained in lichens from different sites. High concentrations of the elements As, Ba, Cd, Co, Cr, Fe, La, Mn, Sb and Zn were found for samples collected in sites located near industries and petrochemical plant. Br and Sb concentrations were also high in lichens from sites affected by vehicular emissions.     

GC Fingerprints Coupled to Pattern-Recognition Multivariate SIMCA Chemometric Analysis for Brazilian Gasoline Quality Studies

ASTM D6729 gas chromatographic fingerprinting coupled to pattern-recognition multivariate soft independent modeling of class analogy (SIMCA) chemometric analysis provides an original and alternative approach to screening Brazilian commercial gasoline quality. SIMCA, was performed on gas chromatographic fingerprints to classify the quality of representative commercial gasoline samples selected by hierarchical cluster analysis and collected over a 5 month period from gas stations in São Paulo State, Brazil. Following an optimized ASTM D6729 gas chromatographic-SIMCA algorithm, it was possible to correctly classify the majority of commercial gasoline samples. The method could be employed for rapid monitoring to discourage adulteration.     

Biomonitoring of coastal regions of São Paulo State,Brazil, using mussels <Emphasis Type="Italic">Perna perna</Emphasis>

The marine environment is constantly affected by anthropic actions, with causes consequent degradation of the waters and marine biota by various discharges of xenobiotics. In the present study, the focus was the study of a region of the marine coast of the State of São Paulo (city of Santos), which is one of the most industrialized parts of Brazil and suffers also from a strong impact of domestic effluents. The mussel Perna perna, very abundant in the coast of the State of São Paulo, Brazil, was selected as the biomonitoring organism for the determination of inorganic elements and a passive biomonitoring was performed. The organisms were collected at two sites in São Paulo State coast: Cocanha beach in Caraguatatuba (mussel farm) and Santos Bay (Itaipu and Palmas). Seasonally, the Perna perna were collected between September/08 and July/09 in each study sites. After removal and sample preparation, the elements As, Co, Cr, Fe, Se and Zn were determined by instrumental neutron activation analysis (INAA) and Cd, Pb and Hg were determined by atomic absorption spectroscopy (AAS) in this organism.     

Sewage sludge ash as an alternative low-cost oxygen carrier for chemical looping combustion

In this paper, novel low-cost oxygen carriers containing Fe₂O₃ are evaluated for use in chemical looping combustion. Sewage sludge ashes and reference samples were prepared and used in cyclic reduction and oxidation experiments in a thermogravimetric analyzer (TG). A gaseous (3 % H₂) fuel and a solid fuel (hard coal) were tested. Three-cycle CLC tests were carried out in the 600–800 °C temperature range and long-term testing was performed at 950 °C. A reactivity study showed that the natural sewage sludge ash sample was stable during the cycling TG tests when hydrogen was used as a fuel at all of the temperatures investigated. Strong temperature effects on the oxygen transport capacity were observed. An one-cycle test at 900 °C showed also that the sewage sludge ash successfully reacted with coal. The oxygen released was fully used for coal combustion, with appreciable reaction rate at temperature of ~750–800 °C, that is significantly lower than that obtained for pure Fe₂O₃-based oxygen carrier. The oxidation reaction was much faster than the reduction reaction. Moreover, the sewage sludge ash showed a low tendency toward agglomeration in the cyclic test, which was superior to the behavior of synthetic materials. The sewage sludge ash exhibited also high mechanical strength, an attrition index of 1 % and a high-temperature resistance of 1,170 °C in a reducing atmosphere. We conclude that sewage sludge ash can be effectively used as a low-cost, valuable oxygen carrier in practical application in chemical looping combustion technology for power generation.     

Time still to restore the polluted Piracicaba river basin

Over the last decades the acceleration of the industrialization and urbanization processes together with the intensive agricultural practices have resulted in an impact on the Piracicaba river basin, state of São Paulo, Brazil. The source rivers drain from an area of low population density, absence of heavy industries, non-significant agriculture, native forest and reforestation, the opposite is found in the middle part of the basin. Samples of riverbed sediments were collected along the basin for chemical analysis. Results showed that the source rivers still preserve their natural characteristics, while the Atibaia river in the middle part shows signs of pollution from the agricultural activity, industrial effluents and urban sewage.     

Kinetic study of pyrolysis of waste water treatment plant sludge

Activated sewage sludge samples obtained from two different waste water treatment plants were investigated by thermogravimetric analysis. Due to a very high content of water in the sludge samples, these had to be dried at 160°C in an electrical oven in order to remove all adsorbed water. To ensure pyrolysis conditions, nitrogen atmosphere was applied. The pyrolysis decomposition process was carried out in the temperature range from ambient temperature to 900°C at three different heating rates: 2 K min⁻¹, 5 K min⁻¹, 10 K min⁻¹. TGA and DTG curves of the decomposition processes were obtained. Temperature of onset decomposition, final temperature of decomposition, maximum decomposition rate, and decomposition temperature were determined by thermogravimetric analysis for both sludge samples used. The main decomposition process takes place at temperatures in the range from 230°C to 500°C. Above this temperature, there are only small changes in the mass loss which are often attributed to the decomposition of carbonates present in the sewage sludge samples. To determine the apparent kinetic parameters such as the activation energy and the preexponential factor, the so called Friedman isoconversional method was used. Because of the requirements of this method, initial and final parts of the decomposition process, where crossings of the decomposition lines occurred, were cut off. Obtained dependencies of the apparent activation energies and preexponential factors as a function of conversion were used backwards to calculate the modeled decomposition process of sewage sludge and the experimental data were in good accordance with the data obtained by simulation.     

Daily dietary selenium intake of selected Brazilian population groups

Due to its essential characteristics, the daily dietary selenium intake of individuals should be monitored accurately. In the current work, daily selenium intake of different Brazilian population groups based on duplicate portion diet analysis was evaluated and compared with the new estimated average requirement values (EAR), to assess if selenium deficiency or excess could be observed in these groups. Selenium content was determined by neutron activation analysis (NAA). The average daily dietary selenium intake found was 26.3 (±8.3) ·g/day for children from the city of São Paulo, 37.4 (±16.0) ·g/day for children from Belém, 107 (±107) ·g/day for children from Macapá, 28.4 (±7.5) ·g/day for institutionalized elderly, 32 (±6) ·g/day for non-institutionalized elderly and 37 (±17) ·g/day for university students from São Paulo. Most daily dietary selenium intake range observed were below the EAR values. The values obtained for children groups from Belém and Macapá cities, whose intake levels were much higher than the recommendation, were an exception.     

TG–MS–FTIR (evolved gas analysis) of kaolinite–urea intercalation complex

The products evolved during the thermal decomposition of kaolinite–urea intercalation complex were studied by using TG–FTIR–MS technique. The main gases and volatile products released during the thermal decomposition of kaolinite–urea intercalation complex are ammonia (NH₃), water (H₂O), cyanic acid (HNCO), carbon dioxide (CO₂), nitric acid (HNO₃), and biuret ((H₂NCO)₂NH). The results showed that the evolved products obtained were mainly divided into two processes: (1) the main evolved products CO₂, H₂O, NH₃, HNCO are mainly released at the temperature between 200 and 450 °C with a maximum at 355 °C; (2) up to 600 °C, the main evolved products are H₂O and CO₂ with a maximum at 575 °C. It is concluded that the thermal decomposition of the kaolinite–urea intercalation complex includes two stages: (a) thermal decomposition of urea in the intercalation complex takes place in four steps up to 450 °C; (b) the dehydroxylation of kaolinite and thermal decomposition of residual urea occurs between 500 and 600 °C with a maximum at 575 °C. The mass spectrometric analysis results are in good agreement with the infrared spectroscopic analysis of the evolved gases. These results give the evidence on the thermal decomposition products and make all explanation have the sufficient evidence. Therefore, TG–MS–IR is a powerful tool for the investigation of gas evolution from the thermal decomposition of materials and its intercalation complexes.     

Status of chemical elements in Atlantic Forest tree species near an industrial complex

Environmental quality assessment studies have been conducted with tree species largely distributed in the Atlantic Forest. Leaf and soil samples were collected in the conservation unit Parque Estadual da Serra do Mar (PESM) nearby the industrial complex of Cubatão, São Paulo State, Brazil, and analyzed for chemical elements by instrumental neutron activation analysis. Results were compared to background values obtained in the Parque Estadual Carlos Botelho (PECB). The higher As, Fe, Hg and Zn mass fractions in the tree leaves of PESM indicated anthropogenic influence on this conservation unit.     

应用TGA-FTIR研究不同来源污泥的燃烧和热解特性

在空气气氛下，利用热重分析方法研究了三种不同来源的污泥燃烧特性。探讨水处理工艺和污泥处理工艺对污泥中有机物的分布影响和燃烧特性影响。研究发现，污水厌氧工艺和污泥厌氧工艺均导致结构复杂、燃烧温度高的有机物生成。在氮气气氛下利用热重红外联用技术，对比研究了同种污泥的热解和燃烧特性，污泥热解主要发生有机物裂解成小分子和小分子的挥发，氧气的存在加速了污泥的裂解。污泥热解温度200℃～500℃，主要气体H2O、CO2、CO以及甲烷等烃类，CO2在高温750℃还存在一个析出峰，由于无机碳酸盐的分解。     

Evaluation of the Anaerobic Co-Digestion of Sewage Sludge and Tomato Waste at Mesophilic Temperature

Sewage sludge is a hazardous waste, which must be managed adequately. Mesophilic anaerobic digestion is a widely employed treatment for sewage sludge involving several disadvantages such as low methane yield, poor biodegradability, and nutrient imbalance. Tomato waste was proposed as an easily biodegradable co-substrate to increase the viability of the process in a centralized system. The mixture proportion of sewage sludge and tomato waste evaluated was 95:5 (wet weight), respectively. The stability was maintained within correct parameters in an organic loading rate from 0.4 to 2.2 kg total volatile solids (VS)/m³ day. Moreover, the methane yield coefficient was 159 l/kg VS (0 °C, 1 atm), and the studied mixture showed a high anaerobic biodegradability of 95 % (in VS). Although the ammonia concentration increased until 1,864?±?23 mg/l, no inhibition phenomenon was determined in the stability variables, methane yield, or kinetics parameters studied.     

Evolved gas analysis of amorphous precursors for S-doped TiO2 by TG-FTIR and TG/DTA-MS

Thermal decomposition of an amorphous precursor for S-doped titania (TiO₂) nanopowders, prepared by controlled sol–gel hydrolysis–condensation of titanium(IV) tetraethoxide and thiourea in aqueous ethanol, has been studied up to 800 °C in flowing air. Simultaneous thermogravimetric and differential thermal analysis coupled online with quadrupole mass spectrometer (TG/DTA-MS) and FTIR spectrometric gas cell (TG-FTIR) have been applied for analysis of released gases (EGA) and their evolution dynamics in order to explore and simulate thermal annealing processes of fabrication techniques of the aimed S:TiO₂ photocatalysts with photocatalytic activities under visible light. The precursor sample prepared with thiourea, released first water endothermically from room temperature to 190 °C, carbonyl sulfide (COS) from 120 to 240 °C in two stages, ammonia (NH₃) from 170 to 350 °C in three steps, and organic mater (probably ether and ethylene) between 140 and 230 °C. The evolution of CO₂, H₂O and SO₂, as oxidation products, occurs between 180 and 240 °C, accompanied by exothermic DTA peaks at 190 and 235 °C. Some small mass gain occurs before the following exothermic heat effect at 500 °C, which is probably due to the simultaneous burning out of residual carbonaceous and sulphureous species, and transformation of amorphous titania into anatase. The oxidative process is accompanied by evolution of CO₂ and SO₂. Anatase, which formed also in the exothermic peak at 500 °C, mainly keeps its structure, since only 10% of rutile formation is detected below or at 800 °C by XRD. Meanwhile, from 500 °C, a final burning off organics is also indicated by continuous CO₂ evolution and small exothermic effects.     

Soils of Azores islands: elemental characterization with an emphasis on rare-earth elements

This work addresses the chemical features of topsoils from Pico, São Jorge and São Miguel islands (Azores, Portugal), resulting from the weathering of more or less recent volcanic materials, namely pyroclastic debris, scoriae and basaltic rocks. The fractions under 64 μm of the surface-soil samples (0–10 cm) were put through k ₀-standardized, instrumental neutron activation analysis (k ₀-INAA), and their contents in 29 chemical elements were determined. Overall, the results show the chemical composition in the top horizon of soils to be correlated with the type of initial material, as well as with the age of formation of the island. The more relevant differences between the surveyed islands are: (1) a positive Ce anomaly in soils from São Miguel, most probably due to the higher age of that island; and (2) a fractionation between heavy and light rare-earth elements (REEs) in São Miguel, not found in the younger Pico and São Jorge. Other than the islands’ age, terrain altitude seems another relevant factor in differentiating the topsoils’ composition.