Debido al limitado número de reservas de petróleo y al incremento de emisiones a la atmósfera de gases contaminantes, la producción de combustibles con un origen fósil está siendo reorientada hacia vías más sostenibles. En este contexto, los biocombustibles llevan jugando un papel importante en las últimas décadas, siendo una potente alternativa a los combustibles convencionales pudiendo llegar a reducir las emisiones netas de carbono en un gran porcentaje (hasta valores cercanos al 90% si se emplean como materia primas residuos lignocelulósicos). Sin embargo, las materias primas empleadas para la producción de estos biocombustibles, al igual que sucede con los productos derivados del petróleo, presentan ciertas impurezas que no son deseables en el producto final, destacando la presencia de metales y metaloides. Bajas concentraciones de estos elementos, incluso por debajo del nivel de mg Kg-1, pueden: (i) reducir la eficiencia de producción y la estabilidad del combustible/biocombustible generado; (ii) generar problemas medioambientales y de salud humana; (iii) envenenar, obstruir y ensuciar catalizadores, además de favorecer la corrosión; (iv) afectar al correcto funcionamiento de los motores de combustión en los que se puede emplear el combustible/biocombustible; (v) algunas de estos elementos pueden ser añadidos para mejorar las propiedades antidetonantes, antioxidantes, anticongelantes, lubricantes o antiespumantes del producto final. Por todo ello, la presente Tesis Doctoral, desarrollada en el Departamento de Química Analítica, Nutrición y Bromatología de la Universidad de Alicante y en colaboración con la empresa energética francesa TotalEnergies, se centra en el desarrollo de nuevas metodologías para el análisis multielemental de materias primas precursoras de biocombustibles y productos ligeros derivados del petróleo mediante el acoplamiento de un sistema de consumo total de muestra, conocido como hTISIS (high temperature Torch Integrated Sample Introduction System). Previamente se hizo un estudio bibliográfico de las distintas metodologías de preparación de muestras empleadas para realizar los análisis de este tipo de muestras orgánicas y también de las técnicas espectrométricas más usadas para la determinación elemental. Una vez conocidas las distintas metodologías de preparación de muestras. Se desarrolló un método de dilución de las muestras empleando xileno como disolvente orgánico para realizar los análisis. Para ello, el sistema de consumo total de muestra, hTISIS, se acopló a un espectrómetro de emisión óptico con plasma acoplado inductivamente (ICP-OES). De tal forma que, aplicando una metodología de inyección segmentada, se pudieron obtener concentraciones con alto nivel de exactitud y bajos límites de detección para un conjunto de 15 elementos. Además, se consiguió mitigar los efectos de matriz relacionados con la forma química del silicio, elemento presente en todas las muestras, específicamente en altas concentraciones (decenas de ppm) en aceites de pirólisis y otros precursores de biocombustibles. En segundo lugar, esta metodología se mejoró mediante el acoplamiento de la hTISIS a un espectrómetro de masas en tándem con plasma acoplado inductivamente (ICP-MS/MS) con el objetivo de poder determinar un mayor número de elementos (pudiendo determinar con exactitud elementos interferidos), reduciendo los límites de detección y pudiendo realizar por primer vez los análisis de estas muestras en un modo de aspiración continuo tras la adicción de oxígeno a la salida del sistema de introducción de muestras. Así, se pudieron cuantificar con exactitud 24 elementos en un set de 36 muestras formado por diversos productos ligeros derivados del petróleo, aceites, grasas animales y aceites de pirólisis.

Hoy en día, las técnicas espectrométricas basadas en plasma de acoplamiento inductivo están reemplazando progresivamente a otras técnicas anteriores para el análisis elemental de rutina. Esta categoría incluye la espectrometría de emisión óptica por plasma de acoplamiento inductivo (Inductively Coupled Plasma Optical Emission Spectrometry, ICP OES) y la espectrometría de masas por plasma de acoplamiento inductivo (Inductively Coupled Plasma Mass Spectrometry, ICP-MS). De hecho, el uso de estas técnicas es muy recomendable para la determinación de elementos a niveles traza y ultratraza en muestras de matriz compleja. A pesar de ser cada vez más interesantes en el análisis químico, ambas técnicas presentan todavía ciertas limitaciones cuando se aplican al análisis de este tipo de muestras. La determinación del analito en este caso es especialmente complicada cuando se encuentra a niveles de concentración traza o inferiores. En primer lugar, una importante limitación de las técnicas basadas en plasma (i.e., ICP OES e ICP-MS) radica en la baja eficiencia de transporte de los sistemas de introducción de muestras líquidas convencionales. Su función es transferir una parte representativa de la muestra al plasma. Para ello, estos sistemas incorporan un nebulizador que transforma la muestra líquida en un aerosol. Posteriormente, el aerosol es transportado hasta el plasma por medio de una corriente de gas. Sin embargo, el porcentaje del aerosol que finalmente llega al plasma es muy bajo. Por lo tanto, una forma de mejorar los parámetros analíticos de calidad es aumentar la eficiencia de transporte del analito al plasma. Por otro lado, un cambio en las propiedades físicas de la muestra modifica la distribución de tamaño de gota del aerosol de la muestra, provocando un cambio en la eficiencia de transporte. Esto ocurre, por ejemplo, cuando se nebuliza una muestra con matriz orgánica. En segundo lugar, otra limitación significativa proviene de las interferencias causadas por las especies concomitantes en la matriz de la muestra. En la mayoría de los casos, la complejidad de la matriz de la muestra interfiere en el análisis y, por tanto, afecta a la calidad de los resultados obtenidos. Los efectos de la matriz pueden eliminarse, o al menos minimizarse, utilizando una metodología de calibración apropiada en el análisis. Sin embargo, las metodologías que se utilizan habitualmente para reducir los efectos de la matriz son lentas, tediosas y consumen un gran volumen de reactivos y de muestra. Una alternativa muy prometedora para eliminar, o al menos reducir, las mencionadas limitaciones de forma práctica y económica es la utilización de sistemas de nebulización múltiples, que permiten la introducción simultánea de varias corrientes líquidas. Estos sistemas no solo presentan una tecnología de nebulización altamente eficiente en términos de la generación del aerosol, sino que suponen un avance hacia la automatización dado que permiten realizar mezclas y/o reacciones químicas en línea. Como resultado de estas características, los sistemas de multinebulización son muy interesantes para múltiples aplicaciones, siendo la más extendida la generación de vapor químico. Esta metodología consiste en transformar el analito en fase gas para aumentar su transferencia al plasma. También es interesante para la reducción de los efectos de la matriz mediante metodologías de calibración en línea, que son más rápidas, simples y económicas que las metodologías convencionales. Una última limitación general del análisis de muestras de matriz compleja, independientemente de la técnica utilizada, es la escasez de materiales de referencia certificados que reproduzcan de forma aproximada las condiciones de la muestra que se va a analizar, de modo que resulten una referencia fiable. En resumen, el principal objetivo de esta tesis es mejorar la capacidad analítica de las técnicas basadas en plasma de acoplamiento inductivo (ICP OES e ICP-MS) y simplificar el proceso analítico en el análisis elemental de muestras con matriz compleja. Esto se consigue mediante el desarrollo y aplicación de metodologías analíticas basadas en el uso de sistemas de nebulización múltiple.

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No description available.

A Direct Simulation Monte Carlo fluid dynamics code named FENIX has been employed to study gas flow-through properties of the inductively coupled plasma mass spectrometer (ICP-MS). Simulation data have been tested against the Navier-Stokes and heat equations in order to see if FENIX functions properly. The Navier-Stokes and heat equations have been constructed from simulation data and are compared term by term. This comparison shows that FENIX is able to correctly reproduce fluid dynamics throughout the ICP-MS simulation, with an exception immediately behind the ICP-MS sampler cone, where the continuum criterion for the Navier-Stokes equation is not met. Testing the data produced by Fenix also shows that this DSMC method correctly produces momentum and thermal boundary layer phenomenon as well. FENIX output data produce statistical fluctuations of about 2%. Limitations occur from fitting data near surfaces, incurring a relative error of about 5%, and fitting data to take second derivatives where fluid velocity gradients are steep, introducing a relative error of about 10%.

Polyethylene terephthalate (PET) is an excellent material for bottling water, beverages, edible oils and other liquids because it is light, tough and transparent. PET bottles are also extensively reused for storage of drinking water, beverages and other liquids and for solar disinfection of microbiologically unsafe drinking water in the tropics. In spite of the usefulness of PET bottles earlier works have reported leaching of antimony and acetaldehyde from the bottle matrix into the liquid contents. Both antimony trioxide and acetaldehyde belongs to Group 2B (possible carcinogens) in the International Agency for Research on Cancer (IARC) carcinogen classification. Additionally acetaldehyde associated with alcoholic beverages (derived from alcoholic beverage and formed endogenously) has recently been upgraded to IARC Group 1 carcinogen (carcinogenic to humans). The research aims to assess the pattern and extent of antimony and acetaldehyde migration from British and Nigerian polyethylene terephthalate bottles into bottle contents under typical use and reuse conditions. The research compares the assessed extents of migration with the current regulations to determine whether the maximum acceptable levels of antimony and acetaldehyde are being exceeded and whether current regulations might need to be reassessed. To achieve these goals the pattern and extent of PET bottle use and reuse in Britain and Nigeria were appraised through survey. The survey revealed that new bottles with contents are typically stored prior to use for periods ranging between one and 7 days, with Nigerians storing for longer periods than British respondents. However storage of up to one year was reported. The extent of bottle reuse was high and similar for the two countries. Nevertheless Nigerian respondents reuse bottles for longer periods than British respondents. The survey findings together with relevant literature were used to design laboratory experiments that assessed the extent of antimony and acetaldehyde migration from PET bottles into water/beverages. A total of 82 brands of bottled water and soft drinks in plastic and glass bottles and in cartons were collected. A few samples from Nigeria in plastic pouches were collected. Materials used in bottling including glass and plastic bottle materials, metal and plastic bottle cap materials and plastic cap lining materials were collected. All samples were collected in supermarkets and shops in Britain and Nigeria except drinking water from taps which was collected in Britain only. Some bottles were aged for the purpose of studying the impact of bottle aging on chemical migration. Other bottles were stored with their contents to study the impact of long term storage of bottle contents on chemical migration. Energy dispersive X-ray spectrometry (EDX) and Raman spectroscopy were used to characterise PET bottle material and other materials associated with water and soft drink bottling. Antimony and other trace metals in water and soft drinks were determined using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). Antimony content of PET and other plastics was determined by microwave digestion and ICP-MS. Acetaldehyde content of water and soft drinks and PET were determined using headspace gas chromatography with flame ionisation detection (GC-FID). Accuracy and precision for determination of antimony and other trace elements in bottle materials and bottle contents were good as recoveries were around 100% and coefficients of variation were less than 15% for all analysis types. Accuracy and precision for determination of acetaldehyde in bottle materials and bottle contents were also good as recoveries were around 100% and coefficients of variation were less than 15% for all analysis types. Impact of long term storage, elevated temperatures, bottle thickness, carbonation, bottle aging and bottle size on migration of antimony and acetaldehyde were also assessed. All plastic bottle materials analysed were found to be PET. Bottle cap materials were either polyethylene or polypropylene. All plastic cap lining materials from Britain and some from Nigeria were found to be ethylene vinyl acetate/polypropylene copolymer. Plastic cap lining materials from some Nigerian soft drinks were identified as polyvinyl chloride. Glass bottle materials analysed were found to be soda-lime glass. Metal bottle caps were identified as tinplate, tin-free-steel coated with chromium or aluminium coated with chromium. The antimony concentration in 32 PET bottle materials from Britain and Nigeria were similar and ranged between 177 and 310 mg/kg with an average of 250±30 mg/kg. The concentration agrees well with the industry reported concentration of between 150 and 350 mg/kg. The concentration of residual acetaldehyde in 25 fresh PET bottle materials from Britain and Nigeria ranged between 0.95 and 12.52 µg/g. The average concentration in British and Nigerian soft drinks PET materials are 4.76 and 2.17µg/g respectively. Concentration of residual acetaldehyde was higher in soft drinks and still water PET materials than in sparkling water materials. The concentration of residual acetaldehyde decreases as the bottle wall material becomes older. Also the thinner the bottle walls the lower the concentration of residual acetaldehyde. Antimony concentration in 47 freshly purchased British bottled water and soft drinks ranged between 0.03 and 6.61µg/L with only one sample going above the EU acceptable limit. Concentrations of other trace elements measured were low except titanium which was detected at part per million levels in soft drinks. Lead content of a Nigerian soft drink in glass bottle stored for 2 months was above the EU acceptable limit for lead. At realistic temperatures of 40 and 60°C antimony concentration in the water remained below the EU acceptable limit even after 48 hours of exposure but the concentration exceeded the limit for most exposures at 80°C. Concentration of antimony in some Nigerian bottled water and soft drinks was above the EU limit after 11 months of storage at room temperature. Aged bottles leach lower amount of antimony than new bottles. Similarly larger bottles leach lower amount of antimony than smaller bottles. The average acetaldehyde concentrations found in British fruit juices, carbonated soft drinks, sparkling water and still water were 5113, 1458, 22 and 8 µg/L respectively. Acetaldehyde was not detected in water bottled in glass. The concentration of acetaldehyde in five fruit juice samples in PET bottles and carton was beyond the EU specific migration limit (SML) of 6mg/kg. Also the tolerable daily intake of acetaldehyde could be exceeded as a result of intake of some soft drinks and fruit juices. Acetaldehyde content in soft drinks increase with storage but the increase cannot be accounted for by the residual acetaldehyde in PET. Acetaldehyde was found to be outgassing from some bottles. It was also found to be capable of migrating from soft drinks into bottle wall. Without replenishment the concentration of acetaldehyde in solution decreases with time. The use of PVC cap lining in Nigeria as found in this study is a cause for concern as PVC is associated with health risk issues. The study recommends actions to ensure that antimony in fruit juices and other bottled products remain within the regulatory standard from bottling to consumption for the purpose of safeguarding the health of consumers. Glass used in bottling should be well scrutinized to ensure that it does not contain high levels of lead or other chemical substances that can cause harm to consumers through migration into contents. PET bottles can safely be used for solar water disinfection without the risk of antimony intake at concentrations above safe limits as water temperature achievable as the result of the technique doesn¿t go beyond 60°C. Also aged bottles are safer to use than new bottles because their chemical leaching was found to be lower than that of new bottles. This study recommends the reassessment of the absence of international guidelines for acetaldehyde in water and foods. The study also recommends that the amount of acetaldehyde that can be added to soft drinks as flavouring agent should be below the specific migration limit (SML) for migration of acetaldehyde from PET bottle into bottle contents. This is essential since the SML was designed to ensure that exposure to acetaldehyde, as a result of intake of bottled water and soft drinks in PET bottles, is below the tolerable daily intake (TDI) for acetaldehyde. As antimony was reported to go beyond the safe limits in some Nigerian bottled water and soft drinks after 11 months of storage this study discourages the use of bottle contents stored for a very long time. / Commonwealth Scholarship Commission in the United Kingdom

The co-evolution of life and the environment stands as a cornerstone in Earth's 4.5-billion-year history. Environmental fluctuations have wielded substantial influence over biological evolution, while life forms have, in turn, reshaped Earth's surface and climate. This dissertation centers on a critical period in Earth's history—the Neoproterozoic Era—when profound environmental shifts potentially catalyzed pivotal eukaryotic evolutionary events. By delving deeper into Neoproterozoic paleoenvironments, I aim at a clearer understanding of life-environment co-evolution in this crucial era. The first chapter focuses on an important juncture—the transition from prokaryote to eukaryote dominance in marine ecosystems during the Tonian Period (1000 Ma to 720 Ma). To assess whether the availability of nitrate, an important macro-nutrient, played a critical role in this evolutionary event, nitrogen isotope compositions (δ¹⁵N) of marine carbonates from the early Tonian (ca. 1000 Ma to ca. 800 Ma) Huaibei Group in North China were measured. The data indicate nitrate limitation in early Neoproterozoic oceans. Further, a compilation of Proterozoic sedimentary δ¹⁵N data, together with box model simulations, suggest a ~50% increase in marine nitrate availability at ~800 Ma. Limited nitrate availability in early Neoproterozoic oceans may have delayed the ecological rise of eukaryotes until ~800 Ma when increased nitrate supply, together with other environmental and ecological factors, may have contributed to the transition from prokaryote-dominant to eukaryote-dominant marine ecosystems. Recognizing the spatial and temporal variations in Neoproterozoic oceanic environments, the second chapter lays the groundwork for a robust stratigraphic framework for the early Tonian Period. Employing the dynamic time warping algorithm, I constructed a global stratigraphic framework for the early Tonian Period using δ¹³C_carb data from the North China, São Francisco, and Congo cratons. This exercise confirms the generally narrow range of δ¹³C_carb fluctuations in the early Tonian, but also confirms the presence of a negative δ¹³C_carb excursion of notable magnitude (~9 ‰) at ca. 920 Ma in multiple records, suggesting that it was global in scope. This negative excursion, known as the Majiatun excursion, is likely the oldest negative excursion in the Neoproterozoic Era and marks the onset of the dynamic Neoproterozoic carbon cycle. Shifting focus to the late Neoproterozoic, the third chapter delves into the origins of Neoproterozoic superheavy pyrite, whose bulk-sample δ³⁴S values are greater than those of contemporaneous seawater sulfate and whose origins remain controversial. Two supervised machine learning algorithms were trained on a large LA-ICP-MS pyrite trace element database to distinguish pyrite of different origins. The analysis validates that two models built on the co-behavior of 12 trace elements (Co, Ni, Cu, Zn, As, Mo, Ag, Sb, Te, Au, Tl, and Pb) can be used to accurately predict pyrite origins. This novel approach was then used to identify the origins of pyrite from two Neoproterozoic sedimentary successions in South China. The first set of samples contains isotopically superheavy pyrite from the Cryogenian Tiesi'ao and Datangpo formations. The second set of samples contains pyritic rims from the Ediacaran Doushantuo Formation; these pyrite rims are associated with fossiliferous chert nodules and do not have superheavy sulfur isotopes. For the superheavy pyrite, the models consistently show high confidence levels in identifying its genesis type, and three out of four samples were inferred to be of sedimentary origins. For the pyritic nodule rims, the models suggest that early diagenetic pyrite was subsequently altered by hydrothermal fluids and therefore shows mixed signals. The third chapter highlights the importance of pyrite trace elements in deciphering and distinguishing the origins of pyrite in sedimentary strata. / Doctor of Philosophy / Understanding how life and the environment have shaped our planet's story over 4.5 billion years is like piecing together an intricate puzzle. On the one hand, changes in the environment kickstarted big shifts in how life evolved. On the other hand, living creatures have also left their mark on Earth's landscapes and climate. This dissertation focuses on unraveling the mysterious Neoproterozoic Era (1 billion to 538 million years ago), a time when Earth saw some of its most dramatic changes. A significant aspect of my investigation delves into the evolutionary dynamics within ancient marine ecosystems. Specifically, I'm exploring a critical juncture when organisms with more complex cellular structures, known as eukaryotes, became ecologically more important than prokaryotic life forms in many aspects of Earth systems. By examining ancient rock formations from China, I have found evidence suggesting that nitrate, a vital nutrient, was scarce in the Neoproterozoic oceans. However, around 800 million years ago, there appears to have been a significant surge in nitrate availability. This surge potentially catalyzed a pivotal phase in evolution, possibly driving the shift from prokaryote to eukaryote dominance in these ancient waters. Second, there is a challenge to delineate a robust timeline for the early Neoproterozoic Era. Imagine trying to piece together a story from a time when there were no calendars or clear dates. Employing advanced statistical methods and comparing chemical signals preserved in carbonate rocks from disparate global locations, I endeavor to craft a coherent timeline for this crucial period. Within this timeline, a noteworthy anomaly in the carbon cycle emerged around 920 million years ago known as the Majiatun excursion. This anomaly represents a significant shift in the Neoproterozoic carbon cycle. Furthermore, my investigation plunges into the geochemistry of sulfur, an important element in shaping ancient marine environments. Certain sedimentary rocks harbor anomalous sulfur isotope signatures in the mineral pyrite (also known as fool's gold), hinting at dramatic environmental transformations during the late Neoproterozoic. Employing advanced analytical techniques and machine learning methodologies, I seek to discern the origins and implications of these anomalous sulfur isotope signals found in pyrite, unraveling their significance in reconstructing the environmental dynamics of ancient oceans.

Induktiv gekoppelte Plasma-Massenspektrometrie mit Laserablation (LA-ICP-MS) wird zunehmend für die Einzelzellanalyse eingesetzt, jedoch wird eine weitere verbreitete Verbreitung durch den geringen Durchsatz behindert. Daher wurde in dieser Arbeit der Durchsatz von Einzelzellen-LA-ICP-MS untersucht und verbessert. Zunächst werden die beiden möglichen Ablationsmodi, Bildgebung und Einzelpunktanalyse (SSA), hinsichtlich ihrer analytischen Gütezahlen (Signal-Rausch-Verhältnis, Präzision, Genauigkeit, Durchsatz) verglichen. Hierfür wurden adhärente 3T3-Fibroblastenzellen mit zwei Metallfarbstoffen angefärbt und mit beiden Methoden mehrere Dutzend Zellen vermessen. SSA zeigte überlegene Eigenschaften hinsichtlich Durchsatz und Nachweisgrenzen. Darüber hinaus wurde gezeigt, dass >400 Zellen analysiert werden müssen, um zufriedenstellende Statistiken für einen quantitativen Vergleich der Ergebnisse zu erhalten, was als zu mühsam befunden wurde. Daher wurde ein Einzelzellen-Arraying-Schritt integriert, um eine automatisierte LA-ICP-MS-Analyse zu ermöglichen. Hierfür wurden zwei Arrayingverfahren getestet: Zunächst wurde das mikrofluidische Arraying von Zellen getestet, jedoch verhinderte das Einklemmen von weichen PDMS-Chips eine erfolgreiche Anwendung, und eine Neugestaltung des Chips wäre erforderlich. Daraufhin wurde eine neuartige Technologie getestet, die auf dem Arraying von Tröpfchen in Verbindung mit der Bilderkennung von Zellen beruht, wobei ein Anordnungsdurchsatz von 550 Zellen pro Stunde und eine beispiellose Einzelzellengenauigkeit (> 99%) gefunden wurde. In einem Proof-of-Principle-Experiment wurde ein Zellarray von THP-1-Suspensionszellen mittels LA-ICP-TOF-MS analysiert und erstmals gleichzeitig endogene und exogene Isotope einzelner Zellen als Isotopen-Fingerabdrücke von Zellen mit Nachweisgrenzen von lediglich wenigen hundert attogramm. Schließlich wurden diese Ergebnisse mit der derzeit gebräuchlichsten Analysemethode Single-Cell (sc)-ICP-MS verglichen. / Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is increasingly used for single-cell analysis. However, a more widespread use of LA-ICP-MS in single cell analysis is hampered by its low throughput. Hence, in this work the throughput of single cell LA-ICP-MS was studied and improved. First, the two possible ablation modes, imaging and single spot analysis (SSA) of single cells using a large laser spot, are compared regarding their analytical figures of merit (signal to noise, precision, accuracy, throughput), as well as regarding ease of operation and data evaluation. For that, adherent 3T3 fibroblast cells were stained with two metal dyes and several dozen cells were measured using both modes. SSA showed superior characteristics regarding throughput and detection limits. Moreover, it was shown that >400 cells must be analyzed to reach satisfactory statistics for a quantitative comparison of results, which would have been too laborious. Thus, a single cell arraying step was integrated to enable automated LA-ICP-MS analysis. Two different arraying methods were evaluated: First, arraying via hydrodynamic front trapping of cells using a microfluidic device was tested, but clamping of soft PDMS-chips prevented successful arraying and it was concluded that a major redesign of the chip is necessary. Secondly, and a novel technology relying on a microdroplet arrayer in conjunction with image recognition of cells was tested and a moderate arraying throughput (550 cells per hour) and an unprecedented single-cell accuracy (>99%) was found. In a proof of principle experiment, a cell array of THP-1 suspension cells was analyzed using LA-ICP-TOF-MS and endogenic and exogenic isotopes of individual cells were detected for the first time simultaneously as isotopic fingerprints of cells with detection limits as low as hundred attogram. Finally, these results were compared to the currently more commonly used analysis method single-cell (sc)-ICP-MS.

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No description available.