Improvements in printing technology have exacerbated the problem of document counterfeiting, prompting the need for analytical techniques that better characterize inks for forensic analysis. In this study, 319 printing inks (toner, inkjet, offset, and intaglio) were analyzed directly on the paper substrate using Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS) and Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS). As anticipated, the high sensitivity of LA-ICP-MS resulted in excellent discrimination (> 99%) between ink samples originating from different sources. Moreover, LA-ICP-MS provided ≥ 90% correct association for ink samples originating from the same source. SEM-EDS resulted in good discrimination for toner and intaglio inks (> 97%) and excellent correct association (100%) for all four ink types. However, the technique showed limited utility for the discrimination of inkjet and offset inks. A searchable ink database, the Forensic Ink Analysis and Comparison System (FIACS), was developed in order to provide a tool that allows the analyst to compare a questioned ink sample to a reference population. The FIACS database provided a correct classification rate of 94-100% for LA-ICP-MS and 67-100% for SEM-EDS. An important consideration in forensic chemistry is the interpretation of the evidence. Typically, a match criterion is used to compare the known and questioned sample. However, this approach suffers from several disadvantages, which can be overcome with an alternative approach: the likelihood ratio (LR). Two LA-ICP-MS glass databases were used to evaluate the performance of the LR: a vehicle windshield database (420 samples) and a casework database (385 samples). Compared to the match criterion, the likelihood ratio led to improved false exclusion rates (< 1.5%) and similar false inclusion rates (< 1.0%). In addition, the LR limited the magnitude of the misleading evidence, providing only weak support for the incorrect proposition. The likelihood ratio was also tested through an inter-laboratory study including 10 LA-ICP-MS participants. Good correct association rates (94-100%) were obtained for same-source samples for all three inter-laboratory exercises. Moreover, the LR showed a strong support for an association. Finally, all different-source samples were correctly excluded with the LR, resulting in no false inclusions.

This thesis aims to investigate the formation of deposits from thermally degraded biodiesel on a hot metal surface under the influence of sodium or copper contaminations. Biodiesel or Fatty Acid Methyl Esters (FAMEs) is a widely utilized biofuel with the potential to replace fossil fuels, however, issues regarding the thermal and oxidative stability prevent the progress of biodiesel for utilization as vehicle fuel. The thermal degradation of biodiesel causes formation of deposits often occurring in the fuel injectors, which could result in reduced engine efficiency, increased emissions and engine wear. However, still have no standard method for evaluation of a fuels’ tendency to form deposits been developed. In this study biodiesel deposits have been formed on aluminum test tubes utilizing a Hot Liquid Process Simulator (HLPS), an instrument based on the principle of the Jet Fuel Thermal Oxidation Tester (JFTOT). Quantitative and qualitative analyses have been made utilizing an array of techniques including Scanning Electron Microscopy (SEM), Gas Chromatography Mass Spectrometry (GCMS) and Attenuated Total Reflectance Fourier Transform Infrared Spectrometry (ATR-FTIR). A multi-factorial trial investigating the effects of sodium hydroxide and copper contaminations at trace levels and the impact of a paraffin inhibitor copolymer additive on three different FAME products, two derived from rapeseed oil and one from waste cooking oil as well as a biodiesel blend with mineral diesel, was conducted.The results exhibited that FAMEs are the major precursor to deposit formation in diesel fuel. The SEM analyses exploited the nature of FAME deposits forming porous structures on hot metal surfaces. Sodium hydroxide proved to participate in the deposit formation by forming carboxylic salts. However, the copper contamination exhibited no enhancing effect on the deposits, possibly due to interference of the blank oil in which copper was received. The paraffin inhibitor functioning as a crystal modifier had significant reducing effect on the deposit formation for all biodiesel samples except for the FAME product derived from waste cooking oil. Further studies are needed in order to investigate the influence of glycerin and water residues to the biodiesel deposit formation. Mechanisms involving oxidative or thermal peroxide formation, polymerization and disintegration have been suggested as degradation pathways for biodiesel. The involvement of oxidation intermediates, peroxides, was confirmed by the experiments performed in this thesis. However, the mechanisms of biodiesel deposit formation are complex and hard to study as the deposits are seemingly insoluble. Nevertheless, ATR-FTIR in combination with JFTOT-processing has potential as standard method for evaluation of deposit forming tendencies of biodiesel.

EDS is a tool for quantitative and qualitative analysis of the materials. In electron microscopy, the energy of the electrons determines the depth of the region where the X-rays come from. By varying the energy of the electrons, the depth of the region where the X-rays come from can be changed. If a thin film is used as a specimen, different quantitative ratios of the elements for different electron energies can be obtained. Unique thickness of a specific film on a specific substrate gives unique energy-ratio diagram so the thickness of a thin film can be calculated by analyzing the fingerprints of the energy-ratio diagram of the EDS data obtained from the film.

Soil structure influences many chemical, biological and physical processes and it is well established that organic carbon acts as a soil binding agent. However, the precise location of organic matter and carbon in relation to structural features within intact samples is unknown. The sensitivity of organic carbon to decomposition is dependent not only upon its intrinsic chemical recalcitrance, but also its location within the soil structure. Soil structure provides organic carbon with chemical and physical protection, the extent of which varies between structural units. Furthermore soil structure is transient, and is sensitive to both environmental changes and physical disturbance, therefore it is difficult to determine and quantify the impact of this dynamic entity upon the storage of organic carbon. To date the majority of research that has advanced our understanding of the role soil structure plays in the storage of organic carbon, has relied upon some form of fractionation technique to separate aggregates from the bulk soil. However this approach has its disadvantages as much of the soil structure is destroyed; clearly when studying the impact of soil structure upon organic carbon-storage it is advantageous to implement any method that minimises disturbance to the soil structure. This study entails removing intact soil samples (through the use of kubiena tins) from long-term agricultural experimental fields at Rothamsted Research, (Hertfordshire, UK) with the aim of comparing and evaluating the location of organic matter and it’s associated organic carbon, in soils with contrasting organic carbon contents and a well documented land-use history. Thin sections will be analysed by integrating conventional micromorphology, image analysis and sub-microscopy combined with microscale chemical analysis scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS). In doing so a new alternative method for analysing the distribution of organic matter and organic carbon is proposed. It was found that agricultural soils, which are the same in all aspects except total-OC content, differ in total organic matter, water release characteristics, aggregate stability and pore size distribution; therefore these differences could be attributed to the relationship between OC and soil structure. The water release curve, aggregate stability and pore size distribution also differed between soils with similar OC-contents but from different land-uses. The analysis of organic matter within intact soil samples provided evidence for the redistribution of organic matter as it is decomposed within the soil structure, for instance, less decomposed organ and tissue forms were located in or near to soil pores while more decomposed amorphous forms were located within the soil matrix. Since the same pattern of redistribution was observed in both agricultural and grassland soil this is likely to be directed by soil macro and micro fauna. It is concluded that since the location of different forms of organic matter is consistent across all soil, organic matter location is not responsible for creating differences in aggregate stability between treatments. Instead the results indicate that the amount and strength of organic carbon bonds and its hydrophobic properties are responsible. Micromorphology results demonstrated an absence of defined aggregation between treatments. Despite the difficulties in the interpretation of aggregation, the results contradict theories of aggregation, which state that aggregates are formed around “fresh” organic matter and it is argued that OM will undergo substantial decomposition before it acts as core for aggregation. Initial SEM-EDS analysis, has shown that in the soil matrix adjacent to organic matter (plant/organ) fragments there is a heightened concentration of C, indicating that these fragments are acting as a source of organic carbon. Interestingly BC, which represent one of the most recalcitrant C forms is also acting as a source of C, although these initial results suggest to a lesser extent than more labile C-sources. This source of organic carbon could stimulate microbial activity thereby enhancing soil structural stability. Alternatively, the release of liable carbon into soil pores may represent one route by which labile carbon enters sub-soil horizons.

The purpose of this study is to understand mineral diagenesis authigenic mineral and the effect of climate on mineral of Pleistocene-Holocene sediment deposits in the Southern Kenya Rift. Lake Magadi unique geologic settings are characterized by extreme alkalinity and high silica activities. The mineralogical analysis was achieved by X-Ray diffraction (XRD) and Scanning Electron Microscopy (SEM) applications. The bulk mineralogy (quartz, halite, calcite) is the same on all localities due to similar volcaniclastics compositions throughout the Kenya Rift Valley. The clay mineralogy significantly differ among the groups of sample localities. The differences reflect different tectonic settings and ambient climate regime. In humid climate at higher elevation detrital clay minerals are abundant (feldspars, phillipsite). At lower elevation like Lake Magadi, the clay fractions dominated by authigenic minerals (zeolites and silicate minerals found with zeolites). These results show the potential of clay minerals as terrestrial climate proxies.

This research evaluates two different Biological Nitrogen Removal (BNR) systems for enhanced nitrogen removal in decentralized wastewater treatment. The first study evaluated the performance of Hybrid Adsorption and Biological Treatment Systems (HABiTS) at the pilot scale with and without stage 1 effluent recirculation. HABiTS is a system developed at the bench scale in our laboratory and was designed for enhanced BNR under transient loading conditions. It consists of two stages; an ion exchange (IX) onto clinoptilolite media coupled with biological nitrification in the aerobic nitrification stage 1 and a Tire-Sulfur Adsorption Denitrification (T-SHAD) system in the anoxic denitrification stage 2. The T-SHAD process incorporates NO3- adsorption onto tire chips and Sulfur Oxidizing Denitrification (SOD) using elemental sulfur as the electron donor for NO3- reduction. Previous bench scale studies evaluated HABiTS performance under transient loadings and found significantly higher removal of nitrogen with the incorporation of adsorptive media in stage 1 and 2 compared with controls (80% compared to 73%) under transient loading conditions. In this study, we hypothesize that a HABiTS system with effluent recirculation in nitrification stage 1 may enhance nitrogen removal performance compared to that without recirculation. The following were the expected advantages of Stage 1 effluent recirculation for enhanced nitrogen removal: 1) Pre-denitrification driven by the mixture of nitrified effluent from stage 1 with high concentrations of biochemical oxygen demand (BOD) septic tank effluent. 2) Moisture maintenance in stage 1 for enhanced biofilm growth. 3) Increased mass transfer of substrates to the biofilm in stage 1. 4) Decreased ratio of BOD to Total Kjeldahl Nitrogen (TKN) in the influent of stage 1. Two side-by-side systems were run with the same media composition and fed by the same septic tank. One had a nitrification stage 1 effluent recirculation component (R-system), which operated at a 7:1 stage 1 effluent recirculation ratio for the first 49 days of the study and at 3:1 beginning on day 50 and one was operated under forward flow only conditions (FF-system). The R system removed a higher percentage of TIN (35.4%) in nitrification stage 1 compared to FF (28.8%) and had an overall TIN removal efficiency of 88.8% compared to 54.6% in FF system. As complete denitrification was observed in stage 2 throughout the study, overall removal was dependent on nitrification efficiency, and R-1 had a significantly higher NH4+ removal (87%) compared to FF-1 (70%). Alkalinity concentrations remained constant from stage 1 to stage 2, indicating that some heterotrophic denitrification was occurring along with SOD, as high amounts of sCOD leached from the tire chips in the beginning of the study, reaching sCOD concentrations of 120-160 mg L-1 then decreasing after day 10 of operation of stage 2. Sulfate concentrations from stage 2 for each side were low until the last 10 days of the study, with an average of 16.43 ± 11.36 mg L-1 SO42--S from R-2 and an average of 16.80 ± 7.98 SO42--S for FF-2 for the duration of the study, however at the end of the study when forward flow rates increased, SO42--S concentrations increased to 32 mg L-1 for R-2 and 40 mg L-1 for FF-2. Similar performance was observed in the FF system as the bench scale reactor tests. The second part of the research focused on the findings from a study of a Particulate Pyrite Autotrophic Denitrification (PPAD) process that uses pyrite as the electron donor and nitrate as the terminal electron acceptor in upflow packed bed bioreactors. The advantages of using pyrite as an electron donor for denitrification include less sulfate production and lower alkalinity requirements compared with SOD. The low alkalinity consumption of the PPAD process led to comparison of PPAD performance with and without oyster shell addition. Two columns were operated side-by-side, one packed with pyrite and sand only (P+S), while another one was packed with pyrite, sand and oyster shell (P+S+OS). Sand was used as a nonreactive biofilm carrier in the columns. My contribution to this research was to carry out Scanning Electron Microscopy-Energy-Dispersive X-Ray Spectroscopy (SEM-EDS) analysis to support the hypothesis that oyster shell contributes to nitrogen removal because it has a high capacity for biofilm attachment. SEM analysis showed that oyster shell has a rough surface, supported by its high specific surface area, and that there was more biofilm attached to oyster shell than pyrite or sand in the influent to the column. EDS results showed a decrease in atomic percentages for pyrite sulfur in the effluent of both columns (59.91% ± 0.10% to 53.94% ± 0.37% in P+S+OS column and to 57.61% ± 4.21% in P+S column). This finding indicated that sulfur was oxidized more than iron and/or the accumulation of iron species on the pyrite surface and supports the coupling of NO3- reduction with pyrite oxidation.

An experimental study on the effect of fuel mixing on the products resulting from hydrothermal liquefaction (HTL) was conducted. The feedstocks used were kraft lignin (KL), GROT (GT) and microalgae cultivated in wastewater (MA). Three sets of mixtures were prepared, each containing two types of feedstocks with a 1:1 ratio: KLGT, MAKL, and MAGT. The experiments were performed using a pilot-scale continuous HTL-system. Elemental analysis CHNO and thermogravimetric analysis were used to determine the ultimate and proximate composition of the samples. Scanning electron microscopy with energy dispersive spectroscopy (SEM/EDS) was used to further analyse the elemental distribution on the hydrochars’ surface. The co-liquefaction effect (CE) was evaluated by comparing the experimental results found for the mixtures with the theoretical values calculated as the average of the respective pure components. The results showed that the yield of light oil was not significantly affected for any mixture. However, the mixtures containing KL showed a lower yield of heavy oil than the predicted value, while a higher yield was found for MAGT. All heavy oils had higher carbon content than expected from the predicted values. Every mixture had a significantly larger yield of hydrochar than what was expected. The increased yield of hydrochar for KLGT was insufficient to compensate for the loss of heavy oil and thus the overall product yield was decrease showing antagonistic interactions in the mixture. The hydrochar from MAGT had the highest ash content, and upon closer inspection with SEM/EDS it showed a much larger phosphorus content than any other hydrochar, even compared to the predicted value. This suggests that an interaction between MA and GROT causes the hydrochar to bind more contaminants and enables it to collect more ash than what would have been achieved from liquefying the components individually. Thus, MAGT showed synergetic effects overall, MAKL had increased carbon recovery but at the cost of heavy oil yield making in a poor choice for HTL, and KLGT showed antagonistic effects in the form of lower yield of biocrude and overall recovery of products. The study highlights that co-liquefaction can potentially have a larger impact on the hydrochar than it does on the biocrude, and that evaluation of hydrochar should be included when examining co-liquefaction

It has been common in forestry and agriculture to drain waterlogged areas through ditching in order to cultivate them. The ditches that drain water are usually connected to some watercourse, such as a river. When the water flow of the river decreases and becomes more still, particles will settle and fall to the bottom of the water body and form sediment. If there is an increasing amount of nutrients and metals transported with the water, it could affect the water quality negatively, since an increased amount of nutrients could result in eutrophication and many metals are toxic in high amounts. In the Sangis River there is an increased amount of sediment deposited at the mouth of the river and inside the estuary, which has resulted in the river and the estuary becoming shallower. The origin of the deposited sediments is believed to partly be from ditching. The residents of the village of Sangis have said that it is difficult to cross the estuary by boat because of the deposited sediments, therefore, their wish is for a channel dredged in the Sangis River and its estuary that they can use. The main aim of this master's thesis was to analyse the geochemical status of the surface water and the sediment in the estuary of the Sangis River and to give recommendations for future actions preventing sedimentation of the river channel. The analyse of the geochemical status of the sediment was achieved by sampling six sediment- cores in the estuary and analysing for different parameters. The analyse of the geochemical status of the surface water was achieved by comparing the water quality regarding metal concentrations in the estuary with other nearby rivers and classifying the concentration of phosphorous in the estuary, to determinate if there was an ongoing eutrophication. The following analyses were conducted for the sediment-cores: Element distribution were analysed with P-XRF, pH and electrical conductivity were measured and loss on ignition was also calculated trough combustion of the sub-samples. The results showed for the P-XRF that the dominating main elements were iron, sulfur, calcium and potassium. Iron and sulfur were correlated to each other in all profiles and had a peak between 20-35 cm in the sediment. This indicated that there could be formation of iron sulfides at that depth. Therefore, sub-sample 4.D was analysed with SEM-EDS instrument and framboidal pyrite (FeS2) was detected in the sample. The results from the pH and conductivity showed that the pH-value varies greatly both with depth and between the sediment cores. However, for the conductivity it could be seen how it peaked at around 20-35 cm in all profiles, with the highest EC-value in profile 4. It could be concluded that the surface water in the estuary contains elevated concentrations of copper and that there is an ongoing eutrophication as well. Due to the eutrophication, it has most likely resulted in an increased amount of aquatic plants during the summer. The increased amount of organic material has probably resulted in oxygen-free bottoms, since all the oxygen has been consumed when the organic material has been decomposed. The formation of framboidal pyrite shows that the redox ladder has reached the two last steps, since framboidal pyrite (FeS2) consists of reduced sulfur and dissolved iron and is formed during anoxic conditions. Reduced sulfur forms when sulfate is reduced in order to oxidize organic matter and dissolved iron forms when iron-oxide hydroxides are reduced in order to oxidize organic matter. If dredging is carried out in the Sangis river and its estuary, oxidation of framboidal pyrite will occur, this could result in formation of acid and leachate of metals that were previously bound to framboidal pyrite. The consequences if it leaches into the river and the estuary is that it creates an acidic environment with elevated metal concentrations, where marine life would find it hard to live. The extent and impact of leached acidity and metals needs to be studied further.

The analysis of 110 automotive paint samples was conducted for the research presented here. Laser-induced breakdown spectroscopy (LIBS) was the central instrument utilized for analysis although scanning electron microscopy / energy dispersive x-ray spectroscopy (SEM/EDS) and Fourier transform infrared spectroscopy - attenuated total reflection (FTIR-ATR) analyses were also performed. Two separate methods of LIBS analysis of samples were used: a cross sectional analysis and a drill down analysis. SEM/EDS analysis focused on the cross section while FTIR-ATR analysis concentrated on the clearcoat layer. Several different data/statistical analyses were evaluated including principal components analysis (PCA), two tailed t-tests based on several different metrics (Hit Quality Index (HQI), Pearson's correlation and Sorenson index), multivariate analysis of variance and receiver operating characteristic (ROC) curves. Full spectrum data analysis from LIBS spectra resulted in 99.7% discrimination between different sample comparisons and 12% between same sample comparisons based on HQI and t-tests. Peak analysis of LIBS spectra resulted in 87.5% discrimination between different sample comparisons and 5% between same sample comparisons based on MANOVA. When combining the results of the FTIR-ATR and SEM/EDS analyses, 88% of the samples could be discriminated.

De två kemiskt nära besläktade metallerna niob (Nb) och tantal (Ta) räknas av Europakommissionen som kritiska råmaterial. Detta på grund av en kraftigt ökad efterfrågan och en geografiskt koncentrerad global produktion av dem. Det här arbetet utgör en del av ett större projekt som bedrivs av EuroGeoSurveys (EGS); GeoERA FRAME, som har till syfte att kartlägga förekomsten av kritiska råmaterial inom EU. Två granitpegmatitiska prov från Kolsva fältspatgruva har undersökts med avseende på deras kemi och mineralogi; dels sådana som tentativt identifierats som kolumbitmineral och dels sådana som innehåller ett samarskitliknande mineral. I arbetet har tre huvudsakliga analysmetoder använts: 1) optisk mikroskopi, 2) svepelektronmikroskopi (SEM) med energidispersiv mikrokemisk analys (EDS), samt 3) pulverröntgendiffraktionsanalys (XRD). De kemiska analyserna som genomfördes på ”kolumbit-proven” visade att de bestod av kolumbit-(Fe), med generell formel AB2O6 och med en järndominans i A-katjonposition och niobdominans i B-katjonposition. Analyserna visad även på förekomst av mineral tillhörande pyroklorsupergruppen. De samarskitartade mineralen uppvisade en partiell likhet med samarskitgruppmineral (generell formel ABO4), men med hög grad av metamiktisering, dåliga stökiometrier, låga REE-halter, samt med varierande järn- och kalciumdominans i tentativ A-katjonposition och niobdominans i B-katjonpositionen. Även aluminiumsilikater, mineral från spinellgruppen samt hematit påvisades. Uppsprickning av de metamikta och spröda samarskitartade mineralen har möjliggjort en fluidmedierad omvandling, vilket bl.a. lett till bildning av sekundär radiogen blyglans. Resultaten av undersökningarna bekräftar att Kolsvapegmatiten representerar ett lokalt niob-tantalmineraliserat system. / The two chemically related metals niobium (Nb) and tantalum (Ta) are classified by the European Commission as critical raw materials. This is due to a highly increased demand and a limited global supply situation for these metals. This work is a part of a larger project run by EuroGeoSurveys (EGS); the GeoERA FRAME, which aims to map the distribution of critical raw materials in the EU. Two granitic pegmatite samples from the Kolsva feldspar mine were studied with regards to their chemistry and mineralogy. They had been tentatively identified as consisting of a columbite mineral and a samarskite-like mineral, respectively. In the project, three main analytical methods have been used: 1) optical microscopy, 2) scanning electron microscopy (SEM) with energy-dispersive spectroscopy (EDS), and 3) powder X-ray diffraction analysis (XRD). The analyses performed on the “columbite samples” indicated that most of them were columbite-(Fe), general formula AB2O6, with an iron dominance in the A-cation position and niobium dominance in the B-cation position. The analyses also indicated the presence of minerals belonging to the pyrochlore supergroup. The analyses of the samarskite-like minerals yielded results showing a partial resemblance to the samarskite group minerals (general formula ABO4), but with a high degree of metamictisation, poor stoichiometries, low to very low REE contents, variable iron and calcium-dominance in a tentative A-cation position and niobium-dominance in the B-cation position. Aluminium silicates, minerals from the spinel group and hematite were also observed in this assemblage. Fracturing of the brittle, metamict samarskite-like minerals have enabled a fluid-mediated alteration, which a.o. led to the formation of secondary radiogenic galena. The study confirms that the Kolsva pegmatite represents a locally Nb-Ta mineralised system.