978 resultados para Trace-element Analysis
Resumo:
Web openings could be used in cold-formed steel beam members, such as wall studs or floor joints, to facilitate ease of services in buildings. In this paper, a combination of tests and non-linear finite element analyses is used to investigate the effect of such holes on web crippling under end-one-flange (EOF) loading condition; the cases of both flanges fastened and unfastened to the bearing plates are considered. The results of 74 web crippling tests are presented, with 22 tests conducted on channel sections without web openings and 52 tests conducted on channel sections with web openings. In the case of the tests with web openings, the hole was either located centred above the bearing plates or having a horizontal clear distance to the near edge of the bearing plates. A good agreement between the tests and finite element analyses was obtained in term of both strength and failure modes.
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During this thesis work a coupled thermo-mechanical finite element model (FEM) was builtto simulate hot rolling in the blooming mill at Sandvik Materials Technology (SMT) inSandviken. The blooming mill is the first in a long line of processes that continuously or ingotcast ingots are subjected to before becoming finished products. The aim of this thesis work was twofold. The first was to create a parameterized finiteelement (FE) model of the blooming mill. The commercial FE software package MSCMarc/Mentat was used to create this model and the programing language Python was used toparameterize it. Second, two different pass schedules (A and B) were studied and comparedusing the model. The two pass series were evaluated with focus on their ability to healcentreline porosity, i.e. to close voids in the centre of the ingot. This evaluation was made by studying the hydrostatic stress (σm), the von Mises stress (σeq)and the plastic strain (εp) in the centre of the ingot. From these parameters the stress triaxiality(Tx) and the hydrostatic integration parameter (Gm) were calculated for each pass in bothseries using two different transportation times (30 and 150 s) from the furnace. The relationbetween Gm and an analytical parameter (Δ) was also studied. This parameter is the ratiobetween the mean height of the ingot and the contact length between the rolls and the ingot,which is useful as a rule of thumb to determine the homogeneity or penetration of strain for aspecific pass. The pass series designed with fewer passes (B), many with greater reduction, was shown toachieve better void closure theoretically. It was also shown that a temperature gradient, whichis the result of a longer holding time between the furnace and the blooming mill leads toimproved void closure.
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Trace Elements (TEs) pollution is a significant environmental concern due to its toxic effects on human and ecosystem health and its potential to bioaccumulate in the food chain and to threaten species survival, leading to a decline in biodiversity. Urban areas, industrial and mining activities, agricultural practices, all contribute to the release of TEs into the environment posing a significant risk to human health and ecosystems. Several techniques have been developed to control TEs into the environment. This work presents the findings of three-year PhD program that focused on research on TEs pollution. The study discusses three fundamental aspects related to this topic from the perspective of sustainable development, environmental and human health. (1) High levels of TEs contamination prevent the use of sewage sludge (SS) as a fertilizer in agriculture, despite its potential as a soil amendment. Developing effective techniques to manage TEs contamination in SS is critical to ensure its safe use in agriculture and promote resource efficiency through sludge reuse. Another purpose of the study was to evaluate different strategies to limit the TEs uptake by horticultural crops (specifically, Cucumis Melo L.). This study addressed the effect of seasonality, Trichoderma inoculation and clinoptilolite application on chromium (Cr), copper (Cu) and lead (Pb) content of early- and late-ripening cultivars of Cucumis Melo L.. Finally, the accumulation of copper and the effect of its bioavailable fraction on bacterial and fungal communities in the rhizosphere soil of two vineyards, featuring two different varieties of Vitis vinifera grown for varying lengths of time, were evaluated.
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Mounting evidence exists that variations in sulphur content in stalagmites are closely linked to changes in volcanic or anthropogenic atmospheric sulphur. The strong dependency of sulphur on soil pH and ecosystem storage, however, can result in a delay of several years to decades in the registration of volcanic eruptions and anthropogenic emissions by stalagmites. Here we present synchrotron-radiation based trace element analysis performed on a precisely-dated section of a stalagmite from Sofular Cave in Northern Turkey. As this section covers the time interval of the intensively studied Minoan volcanic eruption between 1600 and 1650 BC, we can test whether this vigorous eruption can be traced in a stalagmite. Of all measured trace elements, only bromine shows a clear short-lived peak at 1621±251621±25 BC, whereas sulphur and molybdenum show peaks later at 1617±251617±25 and 1589±251589±25 respectively. We suggest that all trace element peaks are related to the Minoan eruption, whereas the observed phasing of bromine, molybdenum and sulphur is related to differences in their retention rates in the soil above Sofular Cave. For the first time, we can show that bromine appears to be an ideal volcanic tracer in stalagmites, as it is a prominent volatile component in volcanic eruptions, can be easily leached in soils and rapidly transferred from the atmosphere through the soil and bedrock into the cave and stalagmite respectively. Highly resolved oxygen and carbon isotope profiles indicate that the Minoan eruption had no detectable climatic and environmental impact in Northern Turkey.
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Volatile organic compounds play a critical role in ozone formation and drive the chemistry of the atmosphere, together with OH radicals. The simplest volatile organic compound methane is a climatologically important greenhouse gas, and plays a key role in regulating water vapour in the stratosphere and hydroxyl radicals in the troposphere. The OH radical is the most important atmospheric oxidant and knowledge of the atmospheric OH sink, together with the OH source and ambient OH concentrations is essential for understanding the oxidative capacity of the atmosphere. Oceanic emission and / or uptake of methanol, acetone, acetaldehyde, isoprene and dimethyl sulphide (DMS) was characterized as a function of photosynthetically active radiation (PAR) and a suite of biological parameters, in a mesocosm experiment conducted in the Norwegian fjord. High frequency (ca. 1 minute-1) methane measurements were performed using a gas chromatograph - flame ionization detector (GC-FID) in the boreal forests of Finland and the tropical forests of Suriname. A new on-line method (Comparative Reactivity Method - CRM) was developed to directly measure the total OH reactivity (sink) of ambient air. It was observed that under conditions of high biological activity and a PAR of ~ 450 μmol photons m-2 s-1, the ocean acted as a net source of acetone. However, if either of these criteria was not fulfilled then the ocean acted as a net sink of acetone. This new insight into the biogeochemical cycling of acetone at the ocean-air interface has helped to resolve discrepancies from earlier works such as Jacob et al. (2002) who reported the ocean to be a net acetone source (27 Tg yr-1) and Marandino et al. (2005) who reported the ocean to be a net sink of acetone (- 48 Tg yr-1). The ocean acted as net source of isoprene, DMS and acetaldehyde but net sink of methanol. Based on these findings, it is recommended that compound specific PAR and biological dependency be used for estimating the influence of the global ocean on atmospheric VOC budgets. Methane was observed to accumulate within the nocturnal boundary layer, clearly indicating emissions from the forest ecosystems. There was a remarkable similarity in the time series of the boreal and tropical forest ecosystem. The average of the median mixing ratios during a typical diel cycle were 1.83 μmol mol-1 and 1.74 μmol mol-1 for the boreal forest ecosystem and tropical forest ecosystem respectively. A flux value of (3.62 ± 0.87) x 1011 molecules cm-2 s-1 (or 45.5 ± 11 Tg CH4 yr-1 for global boreal forest area) was derived, which highlights the importance of the boreal forest ecosystem for the global budget of methane (~ 600 Tg yr-1). The newly developed CRM technique has a dynamic range of ~ 4 s-1 to 300 s-1 and accuracy of ± 25 %. The system has been tested and calibrated with several single and mixed hydrocarbon standards showing excellent linearity and accountability with the reactivity of the standards. Field tests at an urban and forest site illustrate the promise of the new method. The results from this study have improved current understanding about VOC emissions and uptake from ocean and forest ecosystems. Moreover, a new technique for directly measuring the total OH reactivity of ambient air has been developed and validated, which will be a valuable addition to the existing suite of atmospheric measurement techniques.
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In order to obtain a better understanding about the influence of post-depositional diagenesis on speleothem 230Th/U-ages and paleoclimate variability during Marine Isotope Stage (MIS) 5 in northern Germany, four stalagmites from the Riesenberghöhle (RBH) were investigated by thin section analysis, 230Th/U-dating as well as stable oxygen and carbon isotope and laser ablation inductively coupled mass spectrometry (LA-ICPMS) trace element analysis. The RBH is located in the Weser Hills and is one of the northernmost limestone caves in Germany.rnMulti collector (MC) ICPMS 230Th/U-ages and thin section analysis of the RBH stalagmites shows that some growth phases of the stalagmites were diagenetically altered after their deposition. The impact of post-depositional diagenesis (PDD) on the 230Th/U-ages is modeled, and potential processes leading to PDD are discussed. In this context, it is suggested that PDD may be induced by rapid climate change at the inception of the GIS.rnDespite of the dating uncertainties resulting from PDD, 230Th/U-dating shows that the RBH stalagmites grew during the Eemian and most of the Greenland Interstadials (GIS) during MIS 5. Thus, the growth phases of the RBH stalagmites might be related to a reorganization of the Atlantic Meridional Overturning Circulation (AMOC). The stable isotope (δ13C and δ18O) and the trace element variability of the stalagmites reflects rapid changes of past temperature and precipitation on millennial and sub-millennial timescales. These past climate changes can be amplified by orbitally forced variations of the July solar insolation at 65°N.
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Die im Süden der Türkei gelegen, antiken Städte Aspendos und Patara, waren in der Römerzeit zwei bedeutende Handelszentren mit hoher Bevölkerungsdichte. Aquädukte versorgten beide Städte mit carbonathaltigem Wasser, wobei sich Kalksinter (Calciumcarbonat) in der Kanalrinne ablagerte. Dabei lagern sich im Wechsel eine hellere und dunklere Kalksinterlage ab, die als Sinterpaar bezeichnet wird. Um die Entstehung dieser Sinterpaare besser zu verstehen, und die beteiligten Prozesse mit saisonalen Veränderungen der Umwelt zu korrelieren, werden in der vorliegenden Arbeit laminierten Sinterablagerungen mit geochemischen und petrographischen Methoden untersucht.rnEntlang der Kanalrinne beider Aquädukte wurden an mehreren Stellen Proben entnommen. Es wurde untersucht in wieweit sich die Sinterstruktur aufgrund von Änderungen in der Neigung des Wasserkanals oder des Kanaltyps ändert. Um die Kristallform und die kristallografische Orientierung der Kristalle innerhalb der verschiedenen Sinterpaare zu untersuchen, wurden die entnommenen laminierten Kalksinterablagerungen mit Hilfe optischer Mikroskopie und EBSD (Electron Backscatter Diffraction) analysiert. Der Electron Probe Micro-Analyzer (EPMA) wurde verwendet, um saisonale Schwankungen der Hauptelementverteilung und den Anteil der stabilen Isotope im Wasser zu bestimmen. Die LA-ICP-MS (Laser Ablation-induktiv gekoppeltem Plasma-Massenspektrometrie) Spurenelementanalyse wurde durchgeführt, um kleinste Schwankungen der Spurenelemente zu finden. Basierend auf diesen Analysen wurde festgestellt, dass laminierten Kalksinterablagerungen laterale Änderungen in der Aquäduktstruktur und -neigung, jahreszeitliche Änderungen der Wasserchemie, der Temperatur sowie der Entgasungsrate während eines Jahres widerspiegeln. Die Kalksinterablagerungen zeigen eine deutliche Laminierung in Form von feinkörnig-porösen und grobkörnig-dichten Schichten, die trockene und nasse Jahreszeiten anzeigen. Feinkörnige Schichten zeigen eine hohe Epifluoreszenz aufgrund reichhaltiger organischer Inhalte, die vermutlich eine Folge der bakteriellen Aktivität während der warmen und trockenen Jahreszeit sind. Stabile Sauerstoff und Kohlenstoff-Isotop-Kurven entsprechen auch den jahreszeitlichen Schwankungen der verschiedenen Schichtenpaare. Vor allem δ 18O spiegelt jährliche Veränderungen in der Temperatur und jahreszeitliche Veränderungen des Abflusses wieder. Das wichtigste Ergebnis ist, dass die Periodizität von δ 18O durch Erwärmen des Wassers im Wasserkanal und nicht durch die Verdunstung oder der Brunnenwasser-Charakteristik verursacht wird. Die Periodizität von δ 13C ist komplexer Natur, vor allem zeigen δ 18O und δ 13C eine Antikorrelation entlang der Lamellenpaare. Dies wird wohl vor allem durch Entgasungsprozesse im Aquädukt verursacht. Die Ergebnisse der Spurenelemente sind meist inkonsistent und zeigen keine signifikanten Veränderungen in den verschiedenen Lamellenpaaren. Die Isotope Mg, Sr und Ba zeigen hingegen bei einigen Proben eine positive Korrelation und erreichen Höchstwerte innerhalb feinkörnig-poröser Schichten. Auch sind die Hauptelementwerte von Fe, K, Si und anderer detritischer Elemente innerhalb der feinkörnige-porösen Schichten maximal. Eine genaue Datierung der Kalksinterablagerungen ist wünschenswert, da der Zeitraum, in dem die Aquädukte aktiv waren, bereits archäologisch auf 200-300 Jahre festgelegt wurde. Paläomagnetische und 14C-Datierung geben keine brauchbare Ergebnisse. Die U/Th Isotopie wird durch eine hohe Anfangskonzentration von Th in den Proben behindert. Trotz dieser Schwierigkeiten war eine U/Th Datierung an einem Testbeispiel des Béziers Aquädukt erfolgreich. Mit Hilfe von analogen Untersuchungen an aktiven Wasserkanälen der heutigen Zeit, werden die Ablagerungsmechanismen und die geochemische Entwicklung der laminierten Sinterschichten besser verstanden. Ein weiteres laufendes Projekt dieser Doktorarbeit ist die Überwachung von Sinterabscheidungen und der saisonale Zusammensetzung des Wassers an einigen heute noch aktiven Aquädukten. Das Ziel ist die Untersuchung der jetzigen Calciumcarbonatabscheidungen in Aquäduktkanälen unter den heutigen Umgebungsbedingungen. Erste Ergebnisse zeigen, dass kleine regelmäßige jahreszeitliche Veränderungen in der Isotopenzusammensetzung des Wassers vorliegen, und dass die beobachtete Periodizität der stabilen Isotope aufgrund von Änderungen im eigentlichen Kanal entstanden ist. Die Untersuchung von Kalksinterablagerungen in römischen Aquädukten liefern vielversprechende Ergebnisse, für die Untersuchung des Paläöklimas, der Archaeoseismologie und anderer Umweltbedingungen in der Römerzeit. Diese Studie beschränkt sich auf zwei Aquädukte. Die Untersuchungen weiterer Aquädukte und einer Überwachung, der noch in Betrieb stehenden Aquädukte werden genauere Ergebnisse liefern.
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The Al Shomou Silicilyte Member (Athel Formation) in the South Oman Salt Basin shares many of the characteristics of a light, tight-oil (LTO) reservoir: it is a prolifi c source rock mature for light oil, it produces light oil from a very tight matrix and reservoir, and hydraulic fracking technology is required to produce the oil. What is intriguing about the Al Shomou Silicilyte, and different from other LTO reservoirs, is its position related to the Precambrian/Cambrian Boundary (PCB) and the fact that it is a ‘laminated chert‘ rather than a shale. In an integrated diagenetic study we applied microstructural analyses (SEM, BSE) combined with state-of-the-art stable isotope and trace element analysis of the silicilyte matrix and fractures. Fluid inclusion microthermometry was applied to record the salinity and minimum trapping temperatures. The microstructural investigations reveal a fi ne lamination of the silicilyte matrix with a mean lamina thickness of ca. 20 μm consisting of predominantly organic matter-rich and fi nely crystalline quartz-rich layers, respectively. Authigenic, micron-sized idiomorphic quartz crystals are the main matrix components of the silicilyte. Other diagenetic phases are pyrite, apatite, dolomite, magnesite and barite cements. Porosity values based on neutron density logs and core plug data indicate porosity in the silicilyte ranges from less than 2% to almost to 40%. The majority of the pore space in the silicilyte is related to (primary) inter-crystalline pores, with locally important oversized secondary pores. Pore casts of the silica matrix show that pores are extremely irregular in three dimensions, and are generally interconnected by a complex web or meshwork of fi ne elongate pore throats. Mercury injection capillary data are in line with the microstructural observations suggesting two populations of pore throats, with an effective average modal diameter of 0.4 μm. The acquired geochemical data support the interpretation that the primary source of the silica is the ambient seawater rather than hydrothermal or biogenic. A maximum temperature of ca. 45°C for the formation of microcrystalline quartz in the silicilyte is good evidence that the lithifi cation and crystallization of quartz occurred in the fi rst 5 Ma after deposition. Several phases of brittle fracturing and mineralization occurred in response to salt tectonics during burial. The sequences of fracture-fi lling mineral phases (dolomite - layered chalcedony – quartz – apatite - magnesite I+II - barite – halite) indicates a complex fl uid evolution after silicilyte lithifi cation. Primary, all-liquid fl uid inclusions in the fracturefi lling quartz are good evidence of growth beginning at low temperatures, i.e. ≤ 50ºC. Continuous precipitation during increasing temperature and burial is documented by primary two-phase fl uid inclusions in quartz cements that show brines at 50°C and fi rst hydrocarbons at ca. 70°C. The absolute timing of each mineral phase can be constrained based on U-Pb geochronometry, and basin modelling. Secondary fl uid inclusions in quartz, magnesite and barite indicate reactivation of the fracture system after peak burial temperature during the major cooling event, i.e. uplift, between 450 and 310 Ma. A number of fi rst-order trends in porosity and reservoir-quality distribution are observed which are strongly related to the diagenetic and fl uid history of the reservoir: the early in-situ generation of hydrocarbons and overpressure development arrests diagenesis and preserves matrix porosity. Chemical compaction by pressure dissolution in the fl ank areas could be a valid hypothesis to explain the porosity variations in the silicilitye slabs resulting in lower porosity and poorer connectivity on the fl anks of the reservoir. Most of the hydrocarbon storage and production comes from intervals characterized by Amthor et al. 114488 preserved micropores, not hydrocarbon storage in a fracture system. The absence of oil expulsion results in present-day high oil saturations. The main diagenetic modifi cations of the silicilyte occurred and were completed relatively early in its history, i.e. before 300 Ma. An instrumental factor for preserving matrix porosity is the diffi culty for a given slab to evacuate all the fl uids (water and hydrocarbons), or in other words, the very good sealing capacity of the salt embedding the slab.
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A geochemical, mineralogical, and isotopic database comprising 75 analyses of Ocean Drilling Program (ODP) Leg 193 samples has been prepared, representing the variable dacitic volcanic facies and alteration types observed in drill core from the subsurface of the PACMANUS hydrothermal system (Table T1. The data set comprises major elements, trace and rare earth elements (REE), various volatiles (S, F, Cl, S, SO4, CO2, and H2O), and analyses of 18O and 86Sr/87Sr for bulk rock and mineral separates (anhydrite). Furthermore, normative mineral proportions have been calculated based on the results of X-ray diffraction (XRD) analysis (Table T2) using the SOLVER function of the Microsoft Excel program. Several of the samples analyzed consist of mesoscopically distinctive domains, and separate powders were generated to investigate these hand specimen-scale heterogeneities. Images of all the samples are collated in Figure F1, illustrating the location of each powder analyzed and documenting which measurements were performed.
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The Kerguelen Plateau and Broken Ridge in the southern Indian Ocean together represent one of the most voluminous large igneous provinces (LIPs) ever emplaced on Earth. A scientific objective of Ocean Drilling Program (ODP) Leg 183 was to constrain the post-melting magma evolution of Kerguelen Plateau magmas. In an effort to better understand this evolution, isotopic and trace element analysis of individual plagioclase crystals hosted within two Kerguelen Plateau basalts recovered from Elan Bank were undertaken. Previous whole-rock studies established that the two host basalts investigated in this study are samples of crustally contaminated (lower group) and relatively uncontaminated (upper group) basalt. Plagioclase phenocrysts from the uncontaminated basalt are dominantly normal zoned and exhibit a 87Sr/86SrI range of 0.704845-0.704985, which overlaps uncontaminated group whole-rock values previously reported. Plagioclase crystals from the contaminated basalt are dominantly reverse zoned and exhibit a 87Sr/86SrI range of 0.705510-0.705735, which all lie within contaminated group whole-rock values previously reported. There are no systematic within crystal core to rim variations in 87Sr/86SrI from either group, with the exception that contaminated group crystal rims have overall less radiogenic 87Sr/86SrI than other zones. These observations indicate that crustal assimilation occurred before the formation of Unit 10 plagioclase phenocrysts, which is supported by parent magma trace element abundance data inverted using carefully calculated partition coefficients. Trace element diffusion modeling indicates that the upper group basalt (Unit 4) experienced a more vigorous eruptive flux than the lower group basalt (Unit 10). We suggest that plagioclase phenocrysts in both the upper and lower group basalts originated from the shallowest section of what was likely a complex magma chamber system. We contend that the magmatic system contained regions of extensive plagioclase-dominated crystal mush. Crustal assimilation was not a significant ongoing process in this portion of the Elan Bank magmatic system. Both basalts exhibit compelling evidence for remobilization and partial resorption of crystalline debris (e.g., reverse zoned crystals, glomerocrysts). We suggest Unit 4 and 10 magmas ascended different sections of the Elan Bank magma system, where the Unit 10 magmas ascended a section of the magma system that penetrated a stranded fragment of continental crust.
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Manganese nodules occurring within marine sediments of presumably Upper Miocene-Lower Pliocene age from cores obtained by the Argentine oceanographic vessel ARA Islas Orcadas in 1977 on the Malvinas (Falkland) Plateau and neighbouring Scotia Sea were studied with the aim of comparing them with other fossil nodules found on the mainland of Argentina that were also ascribed to the marine environment. After optical mineralogical, chemical, X-ray and trace element analysis, the studied "nodules" proved to be actually wacke clasts cemented by manganese oxides with a high Fe/Mn ratio corresponding to a continental environment. The studied "nodules" thus differ from the Argentine mainland nodules and are supposed to have been transported from continental environments and then deposited in the marine realms. The wacke clasts became then nuclei for the deposition of the marine manganese oxides of the coatings. The proportion of trace elements, which is high, suggests the growth of the nodules in the marine environment.
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Airborne particulate matter (PM) is of environmental concern not only in urban but also rural areas that are easily inhalable and have been considered responsible, together with gaseous pollutants, for possible health effects. The objectives of this research study is to generate an extensive data set for ambient PM collected at Belle Glade and Delray Beach that ultimately was used together with published source profiles to predict the contributions of major sources to the overall airborne particle burden in Belle Glade and Delray Beach. ^ The size segregated particle sampling was conducted for one entire year. The samples collected during the months of January and May were further subjected to chemical analysis for organic compounds by Gas Chromatography-Mass Spectrometry. Additional, PM10 sampling was conducted simultaneously with size segregated particle sampling during January and May to analyze for trace elements using Instrumental Neutron Activation Analysis technique. Elements and organic marker compounds were used in Chemical Mass Balance modeling to determine the major source contribution to the ambient fine particle matter burden. ^ Size segregated particle distribution results show bimodal in both sampling sites. Sugarcane pre-harvest burning in the rural site elevated PM10 concentration by about 30% during the sugarcane harvest season compared to sugarcane growing season. Sea salt particles and Saharan dust particles accounted for the external sources. ^ The results of trace element analysis show that Al, Ca, Cs, Eu, Lu, Nd, Sc, Sm, Th, and Yb are more abundant at the rural sampling site. The trace elements Ba, Br, Ce, Cl, Cr, Fe, Gd, Hf, Na, Sb, Ta, V, and W show high abundance at the urban site due to anthropogenic activities except for Na and Cl, which are from sea salt spray. On the other hand, size segregated trace organic compounds measurements show that organic compounds mainly from combustion process were accumulated in PM0.95. ^ In conclusion, major particle sources were determined by the CMB8.2 software as follows: road dust, sugarcane leaf burning, diesel-powered and gasoline powered vehicle exhaust, leaf surface abrasion particles, and a very small fraction of meat cooking. ^