Timing and chemistry of fluid-flow events in the Lawn Hill Platform, Northern Australia

Mudrocks and carbonates of the Isa superbasin in the Lawn Hill platform in northern Australia host major base metal sulfide mineralization, including the giant strata-bound Century Zn-Pb deposit. Mineral paragenesis, stable isotope, and K-Ar dating studies demonstrate that long-lived structures such as the Termite Range fault acted as hot fluid conduits several times during the Paleoproterozoic and Mesoproterozoic in response to major tectonic events. Illite and chlorite crystallinity studies suggest the southern part of the platform has experienced higher temperatures (up to 300 degrees C) than similar stratigraphic horizons in the north. The irregular downhole variation of illite crystallinity values provides further information oil the thermal regime in the basin and shows that clay formation was controlled not only by temperature increase with depth but also by high water/rock ratios along relatively permeable zones. K-Ar dating of illite, in combination with other data, may indicate three major thermal events in the central and northern Lawn Hill platform Lit 1500, 1440 to 1400, and 1250 to 1150 Ma. This study did not detect the earlier Century base metal mineralizing event at 1575 Ma. 1500 Ma ages are recorded only in the south and correspond to the age of the Late Isan orogeny and deposition of the Lower Roper superbasin. They may reflect exhumation of a provenance region. The 1440 to 1300 Ma ages are related to fault reactivation and a thermal pulse at similar to 1440 to 1400 Ma possibly accompanied by fluid flow, with subsequent enhanced cooling possibly due to thermal relaxation or further crustal exhumation. The youngest thermal and/or fluid-flow event at 1250 to 1150 Ma is recorded mainly to the cast of the Tern-lite Range fault and may be related to the assembly of the Rodinian supercontinent. Fluids in equilibrium with illite that formed over a range of temperatures, at different times in different parts of the platform. have relatively uniform oxygen isotope compositions and more variable hydrogen isotope compositions (delta O-18 = 3.5-9.7 parts per thousand V-SMOW; delta D = -94 to -36 parts per thousand V-SMOW). The extent of the 180 enrichment and the variably depleted hydrogen isotope compositions suggest the illite interacted with deep-basin hypersaline brines that were composed of evaporated seawater and/or highly evolved meteoric water. Siderite is the most abundant iron-rich gangue phase in the Century Zn-Pb deposit, which is surrounded by all extensive ferroan carbonate alteration halo. Modeling suggests that the ore siderite formed at temperatures of 120 degrees to 150 degrees C, whereas siderite and ankerite in the alteration halo formed at temperatures of 150 degrees to 180 degrees C. The calculated isotopic compositions of the fluids are consistent with O-18-rich basinal brines and mixed inorganic and organic carbon Sources (6180 = 3-10 parts per thousand V-SMOW, delta C-13 = -7 to -3 parts per thousand V-PDB). in the northeast Lawn Hill platform carbonate-rich rocks preserve marine to early diagenetic carbon and oxygen isotope compositions, whereas ferroan carbonate cements in siltstones and shales in the Desert Creek borehole are O-18 and C-13 depleted relative to the sedimentary carbonates. The good agreement between temperature estimates from illite crystallinity and organic reflectance (160 degrees-270 degrees C) and inverse correlation with carbonate delta O-18 values indicates that organic maturation and carbonate precipitation in the northeast Lawn Hill platform resulted from interaction with the 1250 to 1150 Ma fluids. The calculated isotopic compositions of the fluid are consistent with evolved basinal brine (delta O-18 = 5.1-9.4 parts per thousand V-SMOW; delta C-13 = -13.2 to -3.7 parts per thousand V-PDB) that contained a variable organic carbon component from the oxidation and/or hydrolysis of organic matter in the host sequence. The occurrence of extensive O-18- and C-13-depleted ankerite and siderite alteration in Desert Creek is related to the high temperature of the 1250 to 1150 Ma fluid-flow event in the northeast Lawn Hill platform, in contrast to the lower temperature fluids associated with the earlier Century Zn-Pb deposit in the central Lawn Hill platform.

Zinc deposits and related mineralization of the Burketown mineral field, including the world-class Century Deposit, Northern Australia: Fluid inclusion and stable isotope evidence for basin fluid sources

The stratiform Century Zn-Pb deposit and the discordant Zn-Pb lode deposits of the Burketown mineral field, northern Australia, host ore and gangue minerals with primary fluid inclusions that have not been affected by the Isan orogeny, thus providing a unique opportunity to investigate the nature of the ore-forming brines. All of the deposits are hosted in shales and siltstones belonging to the Isa superbasin and comprise sphalerite, pyrite, carbonate, quartz, galena, minor chalcopyrite, and minor illite. According to Pb model ages, the main ore stage of mineralization at Century formed at I575 Ma, some 20 m.y. after deposition of the host shale sequence. Microthermometry on undeformed, primary fluid inclusions hosted in porous sphalerite shows that the Zn at Century was transported to the deposit by a homogeneous, Ca2+- and Na+-bearing brine with a salinity of 21.6 wt percent NaCl equiv. delta D-fluid of the fluid inclusion water ranges from -89 to -83 per mil, consistent with a basinal brine that evolved from meteoric water. Fluid inclusion homogenization temperatures range between 74 degrees and 125 degrees C, which are lower than the 120 degrees to 160 degrees C range calculated from vitrinite reflectance and illite crystallinity data from the deposit. This discrepancy indicates that mineralization likely formed at 50 to 85 Mpa, corresponding to a depth of 1,900 to 3,100 m. Transgressive galena-sphalerite veins that cut stratiform mineralization at Century and breccia-filled quartz-dolomite-sphalerite-galena veins in the discordant Zn-Pb lodes have Pb model ages between 1575 and 1485 Ma. Raman spectroscopy and microthermometry reveal that the primary fluid inclusions in these veins contain Ca2+, Na+. but they have lower salinities between 23 and 10 wt percent NaCl equiv and higher delta D-fluid values ranging from -89 to -61 per mil than fluid inclusions in porous sphalerite from Century. Fluid inclusion water from sphalerite in one of the lode deposits has delta O-18(fluid) values of 1.6 and 2.4 per mil, indistinguishable from delta O-18(fluid) values between -0.3 to +7.4 per mil calculated from the isotopic composition of coexisting quartz, dolomite, and illite. The trend toward lower salinities and higher delta D-fluid values relative to the earlier mineralizing fluids is attributed to mixing between the fluid that formed Century and a seawater-derived fluid from a different source. Based on seismic data from the Lawn Hill platform and paragenetic and geochemical results from the Leichhardt River fault trough to the south, diagenetic aquifers in the Underlying Calvert superbasin appear to have been the most likely sources for the fluids that formed Century and the discordant lode deposits. Paragenetically late sphalerite and calcite cut sphalerite, quartz, and dolomite in the lode deposits and contain Na+-dominated fluid inclusions with much lower salinities than their older counterparts. The isotopic composition of calcite also indicates delta O-18(fluid) from 3.3 to 10.7 per mil, which is larger than the range obtained from synmineralization minerals, supporting the idea that a unique fluid source was involved. The absolute timing of this event is unclear, but a plethora of Pb model, K-Ar, and Ar-40/Ar-39 ages between 1440 and 1300 Ma indicate that a significant volume of fluid was mobilized at this time. The deposition of the Roper superbasin from ca. 1492 +/- 4 Ma suggests that these late veins formed from fluids that may have been derived from aquifers in overlying sediments of the Roper superbasin. Clear, buck, and drusy quartz in veins unrelated to any form of Pb-Zn mineralization record the last major fluid event in the Burketown mineral field and form distinct outcrops and ridges in the district. Fluid inclusions in these veins indicate formation from a low-salinity, 300 degrees +/- 80 degrees C fluid. Temperatures approaching 300 degrees C recorded in organic matter adjacent to faults and at sequence boundaries correspond to K-Ar ages spanning 1300 to 1100 Ma, which coincides with regional hydrothermal activity in the northern Lawn Hill platform and the emplacement of the Lakeview Dolerite at the time of assemblage of the Rodinia supercontinent.

Spectroscopic analysis of terrestrial analogues for the interpretation of surface composition of rocky bodies in the solar system. Effects of mineral mixing and particle size. Applications to moon, mars and implications for mercury.

Among the Solar System’s bodies, Moon, Mercury and Mars are at present, or have been in the recent years, object of space missions aimed, among other topics, also at improving our knowledge about surface composition. Between the techniques to detect planet’s mineralogical composition, both from remote and close range platforms, visible and near-infrared reflectance (VNIR) spectroscopy is a powerful tool, because crystal field absorption bands are related to particular transitional metals in well-defined crystal structures, e.g., Fe2+ in M1 and M2 sites of olivine or pyroxene (Burns, 1993). Thanks to the improvements in the spectrometers onboard the recent missions, a more detailed interpretation of the planetary surfaces can now be delineated. However, quantitative interpretation of planetary surface mineralogy could not always be a simple task. In fact, several factors such as the mineral chemistry, the presence of different minerals that absorb in a narrow spectral range, the regolith with a variable particle size range, the space weathering, the atmosphere composition etc., act in unpredictable ways on the reflectance spectra on a planetary surface (Serventi et al., 2014). One method for the interpretation of reflectance spectra of unknown materials involves the study of a number of spectra acquired in the laboratory under different conditions, such as different mineral abundances or different particle sizes, in order to derive empirical trends. This is the methodology that has been followed in this PhD thesis: the single factors previously listed have been analyzed, creating, in the laboratory, a set of terrestrial analogues with well-defined composition and size. The aim of this work is to provide new tools and criteria to improve the knowledge of the composition of planetary surfaces. In particular, mixtures composed with different content and chemistry of plagioclase and mafic minerals have been spectroscopically analyzed at different particle sizes and with different mineral relative percentages. The reflectance spectra of each mixture have been analyzed both qualitatively (using the software ORIGIN®) and quantitatively applying the Modified Gaussian Model (MGM, Sunshine et al., 1990) algorithm. In particular, the spectral parameter variations of each absorption band have been evaluated versus the volumetric FeO% content in the PL phase and versus the PL modal abundance. This delineated calibration curves of composition vs. spectral parameters and allow implementation of spectral libraries. Furthermore, the trends derived from terrestrial analogues here analyzed and from analogues in the literature have been applied for the interpretation of hyperspectral images of both plagioclase-rich (Moon) and plagioclase-poor (Mars) bodies.

On the validity of subjective measures of company performance

Subjective measures of company performance are widely used in research and typically are interpreted as equivalent to objective measures. Yet, the assumption of equivalence is open to challenge. We compared the use of both types of measure in 3 separate samples. Findings were consistent in showing that: (a) subjective and objective measures of company performance were positively associated (convergent validity); (b) those relationships were stronger than those between measures of differing aspects of performance using the same method (discriminant validity); and (c) the relationships of subjective and objective company performance measures with a range of independent variables were equivalent (construct validity).

The role of accounting in planning and control: with special reference to the Egyptian iron and steel company Hadisolb

This thesis investigates the role of accounting in planning and control in the Egyptian Iron and Steel Company "Hadisolb". The hypothesis is that there should be planning and control at appropriate levels, with a significant accounting involvement, In an organisation such as the Egyptian Iron and Steel Company "Hadisolb" . Part One of the thesis explains the role of accounting in planning and control, with special emphasis on its role in long-range corporate planning and control. Parts Two and Three review the history of the Egyptian Iron and Steel Company "Hadisolb", its organisation and structure, also the role of accounting in its planning and control arrangements, together with comments and criticisms concerning this. Part Four is mainly recommendations for alterations or improvements in planning and control in Hadisolb. This includes a suggested planning and organisation structure, physical and cost control reporting structures.

Avaliação da potencialidade de incorporação de um lodo de uma indústria de produtos de limpeza como adição mineral em concretos de cimento Portland

The generation of industrial wastes has been increased more and more in recent decades, motivating studies about a correct sustainable allocation and that also represents advantages for their generators. In this context, are included two companies of cleaning products niche, located in São José do Mipibu/RN, that produces industrial sludge at a sewage treatment plant, and that is the main approach of this research. Given this, it was studied the incorporation potentiality of this sludge as a mineral addition in cement matrix for concrete production due it high capacity of wastes immobilization inside this material, which are subsequently used in the company for making precast articles. Were added different sludge concentrations (5, 10, 15 and 20%) in a common trait (1: 2: 3), and evaluated their techniques and microstructural implications via workability test in fresh state and compressive strength, full porosity and scanning electron microscopy (SEM) in the hardened state. The results demonstrated the feasibility of the process both from a technical and environmental view as economical. All concretes produced with residue showed an increase of workability given the nature of the waste that had surfactants substances capable of adsorbing tiny particles of air into the batter. However, for all concentrations were obtained lower compressive resistances than standard concrete, with a reduction of 39% for samples with 20% of sludge. This are attributed mainly to an increase of porosity in the transition zone of these material, resulting from increased formation of ettringite at the detriment to the formation of other compounds, but which still allows the use of these for the manufacture of concrete articles with non-structural nature, such as precast floor. In addition, the water absorption and void ratio increased slightly for all samples, except the concrete with 20% of waste that has a reduction for the last parameter. Given this context, the recommended maximum level is 20%, constituting a significant proportion and able to allocate sustainably all waste generated in the industry.

Mineralogy, mineral chemistry, and genesis of precious metal-bearing volcanogenic massive sulfide deposits in the Newfoundland Appalachians, Canada: the Ming deposit as example

The Ming deposit, Newfoundland Appalachians, is a metamorphosed (upper greenschist to lower amphibolite facies), Cambro-Ordovician, bimodalmafic volcanogenic massive sulfide (VMS) deposit that consists of several, spatially-associated, elongated orebodies composed of stratabound semimassive to massive sulfides and/or discordant sulfide stringers in a rhyodacitic footwall. Copper is the main commodity; however, the deposit contains precious metal-bearing zones with elevated Au grades. In this study, field observations, microscopy, and micro-analytical tools including electron microprobe, laser ablation inductively coupled plasma mass spectrometry, and secondary ion mass spectrometry were used to constrain the relative timing of precious metal emplacement, the physico-chemical conditions of hydrothermal fluid precipitation, and the sources of sulfur, precious metals, semi-metals and metals. The ore mineral assemblage is complex and indicates an intermediate sulfidation state. Pyrite and chalcopyrite are the dominant ore minerals with minor sphalerite and pyrrhotite, and trace galena, arsenopyrite and cubanite. Additional trace phases include tellurides, NiSb phases, sulfosalts, electrum, AgHg±Au alloys, and oxides. Silver phases and precious metals occur predominantly in semi-massive and massive sulfides as free grains, and as grains spatially associated with arsenopyrite and/or sulfosalts. Precious metal phases occurring between recrystallized pyrite and within cataclastic pyrite are rare. Hence, the complex ore assemblage and textures strongly suggest syngenetic precious metal emplacement, whereas metamorphism and deformation only internally and locally remobilized precious metal phases. The ore assemblage formed from reduced, acidic hydrothermal fluids over a range of temperatures (≈350 to below 260ºC). The abundance of telluride and Ag-bearing tetrahedrite, however, varies strongly between the different orebodies indicating variable ƒTe₂, ƒSe₂, mBi, and mSb within the hydrothermal fluids. The variations in the concentrations of semi-metals and metals (As, Bi, Hg, Sb, Se, Te), as well as Au and Ag, were due to variations in temperature but also to a likely contribution of magmatic fluids into the VMS hydrothermal system from presumably different geothermal reservoirs. Sulfur isotope studies indicate at least two sulfur sources: sulfur from thermochemically-reduced seawater sulfate and igneous sulfur. The source of igneous sulfur is the igneous footwall, direct magmatic fluid/volatiles, or both. Upper greenschist to lower amphibolite metamorphic conditions and deformation had no significant effect on the sulfur isotope composition of the sulfides at the Ming deposit.

Upper-Pleistocene terrace deposits in Mediterranean climate: geomorphological and source-rock control on mineral and geochemical signatures (Betic Cordillera, SE Spain)

Mineral and chemical composition of alluvial Upper-Pleistocene deposits from the Alto Guadalquivir Basin (SE Spain) were studied as a tool to identify sedimentary and geomorphological processes controlling its formation. Sediments located upstream, in the north-eastern sector of the basin, are rich in dolomite, illite, MgO and KB2BO. Downstream, sediments at the sequence base are enriched in calcite, smectite and CaO, whereas the upper sediments have similar features to those from upstream. Elevated rare-earth elements (REE) values can be related to low carbonate content in the sediments and the increase of silicate material produced and concentrated during soil formation processes in the neighbouring source areas. Two mineralogical and geochemical signatures related to different sediment source areas were identified. Basal levels were deposited during a predominantly erosive initial stage, and are mainly composed of calcite and smectite materials enriched in REE coming from Neogene marls and limestones. Then the deposition of the upper levels of the alluvial sequences, made of dolomite and illitic materials depleted in REE coming from the surrounding Sierra de Cazorla area took place during a less erosive later stage of the fluvial system. Such modification was responsible of the change in the mineralogical and geochemical composition of the alluvial sediments.

Effect of adding mineral additives to alkali-activated natural pozzolan paste

Natural pozzolans are raw materials from geological deposits with a range of chemical compositions that when combined with suitable alkali activators can be converted to geopolymer cement for concrete production. In this paper the concept of adding mineral additives to enhance the properties of geopolymer cement is introduced. Taftan andesite, a natural Iranian pozzolan, was used to study the effect of adding mineral additives such as kaolinite, lime and other calcined pozzolans on the compressive strength of geopolymer cement under both normal and autoclave curing. Scanning electron microscopy (SEM)/energy dispersive X-ray (EDX) was used to determine the composition of the gel phase in both alkali-activated Taftan pozzolan with and without mineral additions. The work has shown that deficiencies in SiO2, Al2O3 and CaO content in the raw natural pozzolan can be compensated for by adding mineral additives for enhanced properties.

Renar och vindkraft II : Vindkraft i drift och effekter på renar och renskötsel

Utbyggnaden av vindkraft inom renskötselområdet har ökat markant det senaste decenniet, trots att kunskapen om påverkan av vindkraftsetableringar ännu inte är fullt utredd och dokumenterad. I den här rapporten beskriver vi framförallt hur vindkraftparker i driftsfas påverkar renarna och renskötseln i tre olika områden. I Malå sameby har vi studerat kalvningsområdet kring Storliden och Jokkmokkslidens vindkraftparker. I Vilhelmina Norra sameby har vi studerat vinterbetesområdet kring Stor-Rotlidens vindkraftpark, samt Lögdeålandets betesområde med Gabrielsbergets vindkraftpark som används av Byrkije reinbetesdistrikt från Norge. För att få en helhetsbild av hur renarna använder sitt betesområde är det viktigt att studera renarnas betes- och förflyttningsmönster långsiktigt och över hela deras betesområde och inte bara inom det lokala området nära parken. Det är också viktigt att ta hänsyn till att renarnas betesutnyttjande skiftar från år till år och mellan olika årstider beroende på väderlek och andra yttre förutsättningar. Vi vill också understryka vikten av att kombinera den traditionella kunskapen från renskötarna med vedertagna vetenskapliga analysmetoder för att besvara de frågor som är viktiga för att kunna bedriva en hållbar renskötsel. Vi har undersökt renarnas användning av områdena genom att utföra spillningsinventeringar under åren 2009-2015 (endast i Malå sameby), och genom att följa renar utrustade med GPS-halsband under åren 2005-2015. Datat är insamlat före och under byggfas och under driftsfas (för Gabrielsberget finns GPS-data endast för driftsfasen). Vi har analyserat data genom att utveckla statistiska modeller för val av betesområde för varje område där vi har beräknat hur renarna förhåller sig till vindkraftparksområdet före, under och efter byggnation, och på Gabrielsberget när parken varit avstängd under 40 dagar och under drift vid olika renskötselsituationer. Genom intervjuer, möten och samtal, samt information från Gabrielsbergets vindkraftparks kontrollprogram, har vi tagit del av renskötarnas erfarenheter av hur renarnas beteende, och därmed även renskötseln, påverkats av vindkraftsutbyggnaden i respektive område. Våra resultat visar att renarna både på kalvnings- och på vinterbetesområden påverkas negativt av vindkraftsetableringarna (Tabell a). Renarna undviker att beta i områden där de kan se och/eller höra vindkraftsverken och föredrar att vistas i områden där vindkraftverken är skymda. I kalvningsområdet i Malå ökade användningen av skymda områden med 60 % under driftsfas. I vinterbetesområdet på Gabrielsberget, när renarna utfodrades i parken och kantbevakades intensivt för att stanna i parkområdet under driftsfas, ökade användningen av skymda områden med 13 % jämfört med när de inte var utfodrade och fick ströva mer fritt. Resultaten visar också att renarna minskar sin användning av området nära vindkraftparkerna. I kalvningslandet i Malå minskar renarna sin användning av områden inom 5 km från parkerna med 16-20 %. Vintertid vid Gabrielsbergets vindkraftpark undvek renarna parken med 3 km. Våra resultat visar även att renarnas betesro minskar inom en radie på 4 km från vindkraftparkerna under kalvningsperioden och tiden därefter i jämförelse med perioden före byggfas. Exakta avstånd som renarna påverkas beror på förutsättningarna i respektive område, exempelvis hur topografin ser ut eller om området är begränsat av stängsel eller annan infrastruktur. Förändringarna i habitatutnyttjande i våra studieområden blev tydligare när parkerna var centralt belägna i renarnas betesområde, som i kalvningsområdet i Malå eller i vinterbeteslandet på Gabrielsberget, medan det inte var lika tydliga effekter kring Stor-Rotlidens park, som ligger i utkanten av ett huvudbetesområde. Oftast är snöförhållandena bättre ur betessynpunkt högre upp i terrängen än nere i dalgångarna, på grund av stabilare temperatur, vind som blåser bort snötäcket och mer variation i topografin. Därför kan etablering av vindkraftparker i höglänta områden försämra möjligheten att använda sådana viktiga reservbetesområden under vintrar med i övrigt dåliga snöförhållanden, vilka blir allt vanligare i och med klimatförändringarna. Våra resultat tyder inte direkt på att renarna påverkats negativt under dåliga betesvintrar men fler år av studier behövs för att ytterligare klargöra hur vindkraft påverkar renarna under dessa vintrar. Våra studier har visat att etablering av vindkraft har konsekvenser för renskötseln under både barmarkssäsongen och under vintern, men effekterna förmodas få störst inverkan inom vinterbetesområdet där det är svårt att hitta alternativa betesområden för renarna. Under sommaren är betestillgången oftast mindre begränsad och renarna kan lättare hitta alternativa områden. En direkt konsekvens av Gabrielsbergets vindkraftpark som är placerad mitt i ett vinterbetesområde har blivit att renarna behöver tillskottsutfodras och bevakas intensivare för att de inte ska gå ut ur området. När den naturliga vandringen mellan olika betesområden störs för att renarna undviker att vistas i ett område kan det leda till att den totala tillgången till naturligt bete minskar och att man permanent måste tillskottsutfodra, alternativt minska antalet renar. Annan infrastruktur som vägar och kraftledningar påverkar också renarna. Vid Storliden och Jokkmokksliden och vid Stor-Rotliden där data samlats in innan vindkraftparken uppfördes visar våra resultat att renarna undviker de omkringliggande landsvägarna redan innan parkerna etablerades. Vid Stor-Rotliden ökar dock renarna användningen av områden nära vägarna efter att parken är byggd. På Gabrielsberget, där vi endast har data under drifttiden, är renarna närmare vägarna (även stora vägar som E4) när renskötarna minskar på kantbevakningen för att inte hålla renarna nära parken. Detta ökar naturligtvis risken för trafikolyckor och innebär att renskötarna måste bevaka dessa områden intensivare. Sist i rapporten presenterar vi förslag till åtgärder som kan användas för att underlätta arbetet för renskötseln om det är så att en vindkraftpark redan är byggd. Några exempel på åtgärder som är direkt kopplat till parken är att stänga av vägarna in i vindkraftparken för att förhindra nöjeskörning med skoter och bil under den tiden renarna vistas i området samt tät dialog mellan vindkraftsbolag och sameby angående vinterväghållningen av vägarna till och inom vindkraftparken. Andra mer regionala åtgärder för att förbättra förutsättningarna för renskötselarbetet på andra platser för samebyn, kan vara att sätta stängsel längst större vägar och järnvägar (t.ex. E4:an eller stambanan) i kombination med strategiskt utplacerade ekodukter. Detta för att underlätta och återställa möjligheterna till renarnas fria strövning och renskötarnas flytt av renar mellan olika betesområden.   

Scheduling of track inspection and maintenance activities in railroad networks

The U.S. railroad companies spend billions of dollars every year on railroad track maintenance in order to ensure safety and operational efficiency of their railroad networks. Besides maintenance costs, other costs such as train accident costs, train and shipment delay costs and rolling stock maintenance costs are also closely related to track maintenance activities. Optimizing the track maintenance process on the extensive railroad networks is a very complex problem with major cost implications. Currently, the decision making process for track maintenance planning is largely manual and primarily relies on the knowledge and judgment of experts. There is considerable potential to improve the process by using operations research techniques to develop solutions to the optimization problems on track maintenance. In this dissertation study, we propose a range of mathematical models and solution algorithms for three network-level scheduling problems on track maintenance: track inspection scheduling problem (TISP), production team scheduling problem (PTSP) and job-to-project clustering problem (JTPCP). TISP involves a set of inspection teams which travel over the railroad network to identify track defects. It is a large-scale routing and scheduling problem where thousands of tasks are to be scheduled subject to many difficult side constraints such as periodicity constraints and discrete working time constraints. A vehicle routing problem formulation was proposed for TISP, and a customized heuristic algorithm was developed to solve the model. The algorithm iteratively applies a constructive heuristic and a local search algorithm in an incremental scheduling horizon framework. The proposed model and algorithm have been adopted by a Class I railroad in its decision making process. Real-world case studies show the proposed approach outperforms the manual approach in short-term scheduling and can be used to conduct long-term what-if analyses to yield managerial insights. PTSP schedules capital track maintenance projects, which are the largest track maintenance activities and account for the majority of railroad capital spending. A time-space network model was proposed to formulate PTSP. More than ten types of side constraints were considered in the model, including very complex constraints such as mutual exclusion constraints and consecution constraints. A multiple neighborhood search algorithm, including a decomposition and restriction search and a block-interchange search, was developed to solve the model. Various performance enhancement techniques, such as data reduction, augmented cost function and subproblem prioritization, were developed to improve the algorithm. The proposed approach has been adopted by a Class I railroad for two years. Our numerical results show the model solutions are able to satisfy all hard constraints and most soft constraints. Compared with the existing manual procedure, the proposed approach is able to bring significant cost savings and operational efficiency improvement. JTPCP is an intermediate problem between TISP and PTSP. It focuses on clustering thousands of capital track maintenance jobs (based on the defects identified in track inspection) into projects so that the projects can be scheduled in PTSP. A vehicle routing problem based model and a multiple-step heuristic algorithm were developed to solve this problem. Various side constraints such as mutual exclusion constraints and rounding constraints were considered. The proposed approach has been applied in practice and has shown good performance in both solution quality and efficiency.

Otimização e validação de métodos empregando DLLME e DLLME-SFO para a extração simultânea de agrotóxicos multiclasse em água mineral

O Rio Grande Sul destaca-se no cenário nacional como grande produtor de diversas culturas, as quais demandam grande quantidade de agrotóxicos das mais diversas classes químicas e toxicidades. No entanto a intensa utilização destes compostos torna-se uma preocupação devido a possíveis contaminações das águas superficiais e subterrâneas. Em virtude da degradação dos mananciais a água mineral passou a ser uma das fontes mais utilizadas para o consumo humano, pois tem-se a percepção de que a mesma possui melhor qualidade que a água tratada, além disso acredita-se que a mesma esta isenta de substâncias orgânicas prejudiciais à saúde humana. Neste trabalho, foi realizada a determinação dos agrotóxicos atrazina, simazina, imazapique, imazetapir, imidacloprido, ciproconazol, tebuconazol e epoxiconazol em água mineral empregando a Microextração Líquido-Líquido Dispersiva (DLLME), Microextração Líquido-Líquido Dispersiva com Solidificação da Gota Orgânica Flutuante (DLLME-SFO) e Cromatografia Líquida acoplada à Espectrometria de Massas em série com fonte de ionização por Eletronebulização (LC-ESI-MS/MS). Para o método empregando DLLME e LC-ESI-MS/MS foram otimizados alguns fatores como o tipo e volume de solvente extrator e dispersor e pH. Após a otimização dos parâmetros de extração, fragmentação dos compostos e separação cromatográfica, o método foi validado avaliando-se curva analítica, linearidade, limites de detecção e quantificação, precisão (repetitividade e precisão intermediária) e exatidão (recuperação). Todas as curvas analíticas apresentaram valores de r maiores que 0,999. Os Limites de Quantificação (LOQs) para o método estiveram na faixa de 5 a 500 ng L-1. Foram obtidas recuperações entre 102 - 120% para a repetibilidade e entre 92 e 110% para a precisão intermediária, com RSD de 2 a 10% para todos os compostos. Para o método empregando DLLME-SFO e LC-ESI-MS/MS foram avaliados alguns parâmetros que afetam a eficiência da extração como, tipo e volume de solvente extrator e dispersor, força iônica e pH. Nas condições ótimas de extração todas as curvas analíticas apresentaram valores de r maiores que 0,997. Os LOQs para o método variaram entre 12,5 - 125 ng L-1. As recuperações foram entre 70 e 118% para a repetitividade e entre 76 e 95% para a precisão intermediária, com RSD de 2 a 18% para todos os compostos. Com relação ao Efeito Matriz (EM) avaliado para todos os compostos pelos dois métodos, foi observado baixo EM. Isso indicou que não é necessário utilizar a curva analítica preparada no extrato branco da matriz para a quantificação destes analitos. Ambos os métodos foram aplicados para a determinação de resíduos de agrotóxicos em amostras de água mineral provenientes de diferentes regiões do estado do Rio Grande do Sul e não foram encontrados resíduos de agrotóxicos nas amostras analisadas. Os métodos validados apresentaram como principais vantagens baixo consumo de solventes orgânicos e amostra, rapidez, altos fatores de concentração e recuperações dentro da faixa aceitável. Os limites de quantificação dos métodos ficaram abaixo dos limites máximos de resíduos permitidos pela legislação brasileira para agrotóxicos em água mineral.

Iron Transformation Pathways and Redox Micro-Environments in Seafloor Sulfide-Mineral Deposits: Spatially Resolved Fe XAS and delta Fe-57/54 Observations

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9 degrees 50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (RXAS) and X-ray diffraction (mu XRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe -bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of delta Fe-57 values up to 6 parts per thousand. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. These micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits.

Geologia, petrologia, geocronologia e mineralizações sulfetadas do complexo ézio, província mineral de carajás, Brasil

Dissertação (mestrado)—Universidade de Brasília, Instituto de Geociências, Pós-Graduação em Geologia, 2015.

Electron microprobe investigations of metamorphic reactions and mineral growth histories, Kwoiek area, British Columbia

The Kwoiek Area of British Columbia contains a pendant or screen of metamorphosed sedimentary and volcanic rocks almost entirely surrounded by a portion of the Coast Range Batholith, and intruded by several dozen stocks. The major metamorphic effects were produced by the quartz diorite batholithic rocks, with minor and later effects by the quartz diorite stocks. The sequence of important metamorphic reactions in the metasedimentary and metavolcanic rocks, ranging in grade from chlorite to sillimanite, is:

1. chlorite + carbonate + muscovite → epidote + biotite

2. chlorite + carbonate → actinolite + epidote

3. chlorite + muscovite → garnet + biotite

4. chlorite + epidote → garnet + hornblende

5. chlorite + muscovite → garnet + staurolite + biotite

6. chlorite + muscovite → aluminum silicate + biotite

7. muscovite + staurolite → garnet + aluminum silicate + biotite

8. staurolite → garnet + aluminum silicate

Continuous reactions, occurring between reactions 5 and 7, are:

A. chlorite + (high Ti) biotite + Al₂O₃ (from plagioclase?)→ garnet + staurolite + (low Ti) biotite + O₂

B. muscovite (phengitic) → garnet + staurolite +muscovite (less phengitic) + O₂ (?)

Detailed electron microprobe work on garnet, staurolite, biotite, and chlorite shows that:

(1) The garnet porphyroblasts are zoned according to a depletion model, called the Rayleigh depletion model, which assumes equilibrium between the edge of a growing garnet and the minerals which are unzoned, notably biotite, chlorite, and muscovite, but which assumes disequilibrium within the garnet.

(2) The staurolite porphyroblasts are also zoned, and from their zoning patterns reactions A, B, and 5 are documented. Progressive reduction of iron with increasing grade of metamorphism is also inferred from the staurolite zoning patterns.

(3) During a late period of falling temperature garnet continued to grow and the biotite and chlorite reequilibrated. The biotite, chlorite, and garnet edge compositions can vary from point to point in a given thin section, indicating that the volume of equilibrium at the final stage of metamorphism was only a few cubic microns.

(4) The horizon within the garnet that grew at maximum temperature can be identified. The Mg/Fe ratio of this horizon, if the garnet composition is a limiting composition in the Al₂O₃ - K₂O - FeO - MgO tetrahedron, increases systematically with increasing metamorphic grade. Biotite and chlorite compositions also show a general increase in Mg/Fe ratio with increasing metamorphic grade, but staurolite appears to show the reverse effect.

(5) The Mg/Fe ratio at the maximum temperature horizon of the garnet porphyroblasts is a function of its Mn content as evidenced from the study of five garnet-bearing rocks, collected from one outcrop area, with the same assemblage but with differing proportions of minerals.

An important implication of zoned minerals is that the effective composition of a system in a phase lies on the join between the homogeneous minerals (if there are two) and not within three-or- four-phase fields when a zoned mineral, such as garnet or staurolite, is present in the assemblage.

Study of the three aluminum silicates found in the Kwoiek Area showed that a constant pressure change in polymorphs from andalusite to kyanite to sillimanite took place with increasing temperature. This transition series is best explained by the metastable formation of andalusite.

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