Analytical Characterization of complex mixtures, such as crude oil, environmental samples, and biological mixtures, is challenging because of the large diversity of molecular components. Mass spectrometry based techniques are among the most powerful tools for the separation of molecules based on their molecular composition, and the coupling of ion mobility spectrometry has enabled the separation and structural elucidation using the tridimensional structure of the molecule. The present work expands the ability of analytical chemists by furthering the development of IMS-MS instrumentation by coupling Trapped Ion Mobility Spectrometry to Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (TIMS-FT-ICR MS). The TIMS-FT-ICR MS platform combines the high-resolution separation of TIMS, which has mobility resolving powers up to 400, and ultra-high mass resolution of FT-ICR MS, with mass resolving power over 1,000,000. This instrumentation allows the assignment of exact chemical composition for compounds in a complex mixture, as well as measurement of the collision cross-section of the molecule. Herein, the principles of the TIMS separation and its coupling to FT-ICR MS are described, as well as how the platform can be applied to targeted analysis of molecules, and untargeted characterization of complex mixtures. Molecular standards were analyzed by TIMS-MS in order to develop a computational workflow that can be utilized to elucidate molecular structure, using the measured collision cross-section of the ion. This workflow enabled identification of structural, cis/trans isomers, and chelated molecules and provides the basis for unsupervised structural elucidation of a complex mixture, and in particular for the elucidation of hydrocarbons from fossil fuels. In summary, this work presents the coupling of TIMS-FT-ICR MS and provides examples of applications as a proof of concept of the potential of this platform for solving complex analytical challenges.

<p>In this work, a simple, less time consuming electrochemical method in the form of an electrochemical sensor has been developed for the detection of PAHs. The sensor was fabricated by the deposition of silver-gold (1:3) alloy nanoparticles (Ag-AuNPs) on ultrathin overoxidized polypyrrole (PPyox) film which formed a PPyox/Ag-AuNPs composite on glassy carbon electrode (PPyox/Ag-AuNPs/GCE). The silver-gold alloy nanoparticles deposited to form the composite were chemically prepared by simultaneous reduction of silver nitrate (AgNO3) and chloroauric acid (HAuCl4) using sodium citrate and characterized by UV-visible spectroscopy technique which confirmed the homogeneous formation of the alloy nanoparticles.</p>

<p>In this work, a simple, less time consuming electrochemical method in the form of an electrochemical sensor has been developed for the detection of PAHs. The sensor was fabricated by the deposition of silver-gold (1:3) alloy nanoparticles (Ag-AuNPs) on ultrathin overoxidized polypyrrole (PPyox) film which formed a PPyox/Ag-AuNPs composite on glassy carbon electrode (PPyox/Ag-AuNPs/GCE). The silver-gold alloy nanoparticles deposited to form the composite were chemically prepared by simultaneous reduction of silver nitrate (AgNO3) and chloroauric acid (HAuCl4) using sodium citrate and characterized by UV-visible spectroscopy technique which confirmed the homogeneous formation of the alloy nanoparticles.</p>

Magister Scientiae - MSc / Polyaromatic hydrocarbons (PAHs) are ubiquitous environmental pollutants that have been shown to be teratogenic, mutagenic and carcinogenic and pose serious threats to the health of aquatic and human life. Several methods have been developed for their determination such as immunoassay, gas chromatography and high performance liquid chromatography (HPLC) in combination with fluorescence or absorbance detection. However, these methods are known to manifest underlying disadvantages such as complicated pretreatment, high costs and time consuming processes. In this work, a simple, less time consuming electrochemical method in the form of an electrochemical sensor has been developed for the detection of PAHs. The sensor was fabricated by the deposition of silver-gold (1:3) alloy nanoparticles (Ag-AuNPs) on ultrathin overoxidized polypyrrole (PPyox) film which formed a PPyox/Ag-AuNPs composite on glassy carbon electrode (PPyox/Ag-AuNPs/GCE). The silver-gold alloy nanoparticles deposited to form the composite were chemically prepared by simultaneous reduction of silver nitrate (AgNO3) and chloroauric acid (HAuCl4) using sodium citrate and characterized by UV-visible spectroscopy technique which confirmed the homogeneous formation of the alloy nanoparticles. Transmission electron microscopy showed that the synthesized nanoparticles were in the range of 20-50 nm. The properties of the composite formed upon deposition of the nanoparticles on the PPyox film were investigated by electrochemical methods. The PPyox/Ag-AuNPs/GCE sensor showed strong catalytic activity towards the oxidation of anthracene, phenanthrene and pyrene, and was able to simultaneously detect anthracene and phenanthrene in a binary mixture of the two. The catalytic peak currents obtained from square wave voltammetry increased linearly with anthracene, phenanthrene and pyrene concentrations in the range of 3.0 x 10-6 to 3.56 x 10-4 M,3.3 x 10-5 to 2.83 x 10-4 M, 3.3 x 10-5 to 1.66 x 10-4 M and with detection limits of 0.169 μM, 1.59 μM and 2.70 μM, respectively. The PPyox/Ag-AuNPs/GCE sensor is simple, has antifouling properties and is less time consuming with a response time of 4 s. / South Africa

Under våren 2021 upptäcktes förhöjda halter av polyaromatiska kolväten (PAH) i Björklinges dricksvattennät. Då ett vattenprov taget hos användare påvisade halter som låg över Livsmedelsverkets gränsvärden och källan till föroreningen inte identifierats, rekommenderades hushållen i Björklinge att inte använda kranvattnet till mat och dryck under en period. Efter sektionering av nätet och provtagning identifierades en äldre, nyligen reparerad, ledningssträcka av gjutjärn som trolig föroreningskälla. Denna typ av ledning är relativt vanligt förekommande i delar av Uppsala Vattens nät. Syftet med denna studie var att få en djupare förståelse för orsakerna till PAH-föroreningen i Björklinge och bedöma risken för att liknande föroreningar ska hända igen, samt att tillhandahålla ett beslutsunderlag för Uppsala Vattens hantering av äldre gjutjärnsledningar.En litteraturstudie genomfördes och data från Björklinge analyserades. Resultaten av litteraturstudien visade att frisättning av PAH från äldre gjutjärnsrör med korrosionsskydd innehållande stenkolstjära eller bitumen är ett välkänt fenomen. Biofilmen har en skyddande effekt och graden av frisättning kan därför påverkas av faktorer som klorering eller syrehalt i vattnet. Även mekaniskt slitage i form av reparationsarbete och tryckvågor kan leda till förhöjda nivåer av PAH. Korrosion av ledningarna är troligen också en viktig faktor.Utifrån litteraturstudien och resultaten från användarprover tagna i Björklinge respektive Skuttunge kunde det konstateras att problemen i Björklinge hade ett samband med frisättning av PAH från gjutjärnsrör. Vid tidpunkten för studien kunde ökande PAH-halter observeras på vissa platser i ledningsnätet även efter ledningsbytet i Björklinge våren 2021, vilket tydde på fortsatt kontaminering. Inga uppmätta halter i användarprover låg dock över något av Livsmedelsverkets gränsvärden och PAH i dricksvattnet anses inte vara ett stort hälsomässigt problem i dagsläget. Det är däremot viktigt att fortsätta monitorera halterna av PAH i Uppsala Vattens nät då denna typ av problem kan uppstå igen. Man bör också vara försiktig med åtgärder som kan påverka biofilmen samt vara återhållsam med spoling av denna typ av ledningar. De ledningar som identifierats som föroreningskällor bör åtgärdas. Med tanke på ledningarnas stigande ålder, begränsad kunskap om PAH och dess hälsoeffekter, samt WHOs rekommendationer bör man dock initiera ett långsiktigt arbete med att byta ut eller renovera denna typ av ledningar i Uppsala Vattens nät. / During the spring of 2021 elevated levels of polyaromatic hydrocarbons (PAH) were discovered in the drinking water supply network of Björklinge. Levels above the limit set by the Swedish Food Agency were observed in one user sample, which led to the inhabitants of Björklinge being recommended not to use the tap water for drinking or cooking while the source of the contamination was being identified. After sectioning and sampling the network, an older, recently repaired cast iron pipe was identified as the probable source of the contamination. This type of pipe is not uncommon in the drinking water network of Uppsala Vatten. The purpose of this study was to gain a deeper understanding of the causes of the PAH contamination in Björklinge and to determine the risk of similar contaminations happening again. Further, it aimed to provide a basis for future decisions regarding the handling of older cast iron pipes in the drinking water network of Uppsala Vatten.A literature study was done and data from Björklinge was analysed. The results of the literature study showed that the release of PAH from older cast iron pipes with coal tar or bitumen coating is a well-known phenomenon. The biofilm has protective properties, and the degree of PAH release can hence be affected by factors such as chlorination or oxygen concentration of the water. Mechanical wear in the form of repair work or pressure waves can also cause increased levels of PAH in the water.Based on the literature study as well as the results from the user samples of Björklinge and Skuttunge, it could be determined that the PAH contamination in Björklinge was related to the release of PAH from old cast iron pipes. At the time of this study, increasing levels of PAH could be observed in some parts of the drinking water network even after the suspected pipes had been replaced during the spring of 2021. This might indicate that the contamination was still ongoing. However, no samples were above the limits set by the Swedish Food Agency and PAH is currently not considered a major health problem. Despite this, it is important to keep monitoring the levels of PAH in the drinking water since the PAH levels might increase again. It is also important to be careful with measures that might affect the biofilm and when flushing cast iron pipes. The pipes that have already been identified as sources of contamination should be replaced. Given the increasing age of the cast iron pipes, the limited knowledge of PAH and its health effects, as well as the recommendations from the WHO, a long-term plan for how to remove or renovate this type of pipes from the drinking water network of Uppsala Vatten should be initiated.

Exposomics applies metabolomics methods and technologies to the comprehensive analysis of all low molecular weight molecules (< 1.5 kDa) in complex biological samples to characterize the interaction between cellular metabolism and exogenous lifestyle exposures that determine health and quality of life. To fully access the diverse classes of biological molecules related to an individual’s metabolic profile, metabolomics frequently requires the use of complementary analytical platforms, and employs targeted and untargeted molecular profiling strategies to identify biomarkers that are clinically relevant to an individual’s health status. Chapter 2 describes a quinoline-based boronic acid biosensor for N-acetylneuraminic acid that undergoes a striking binding enhancement under strongly acidic conditions. For the first time, this work allows for direct analysis of acidic sugars with high selectivity when using UV absorbance or fluorescence detection based on formation of a highly stable boronate ester complex with metabolites containing an α-hydroxycarboxylate moiety. Chapter 3 describes a targeted analysis of 24 different organic contaminants using GC-MS that can serve as biomarkers of recent smoke exposure following search-and-rescue training exercises by firefighters located at three different sites across the province of Ontario. Importantly, skin and possible respiratory uptake of various polycyclic aromatic hydrocarbons, methoxyphenols, and resin acids was confirmed by peak excretion of several wood smoke biomarkers in urine within 6 h following acute exposure. Chapter 4 applied a cross-platform metabolomics strategy based on CE-MS and GC-MS in order to identify and validate dietary biomarkers in matching plasma and urine samples collected from healthy participants in the pilot Diet and Gene Interaction Study (DIGEST). For the first time, we demonstrate that a panel of metabolites can serve as reliable biomarkers following contrasting Prudent and Western diets over 2 weeks of food provisions, which correlated well with self-reported diet records. This work paves the way for the development of objective biomarkers for accurate assessment of wood smoke exposures, as well as complex dietary patterns as required for new advances in occupational health and nutritional epidemiology. / Dissertation / Doctor of Philosophy (PhD) / Exposomics is an emerging multidisciplinary science aimed at deciphering the complex interactions that impact human health and gene expression, such as lifestyle choices (i.e., habitual diet) and lifelong environmental exposures. There is growing interest in identifying biomarkers that can be readily measured for chronic disease prevention given an alarming global prevalence of obesity and cardiometabolic disorders, including heart disease, type 2 diabetes and cancer. The research in this thesis focuses on developing new analytical methods for identifying and quantifying metabolites that may allow for better assessments of human health, and has contributed to the development of novel biosensors for the targeted analysis of N-acetylneuraminic (sialic) acid and related acidic sugars, as well as high resolution methods for broad spectrum analysis of biotransformed organic contaminants from smoke exposure by GC-MS, and plasma and urinary metabolites that differentiate contrasting Prudent and Western diets and correlate well with self-reported diet records.

Present organic carbon fluxes from an upland peat catchment were quantified through measurement of in-situ direct and indirect greenhouse gas fluxes. To predict future greenhouse gas (GHG) fluxes, peat from eroded (E) and uneroded (U) site of an upland peat catchment was characterized.Composition of peat from E and U sites at the Crowden Great Brook catchment, Peak District Nation Park, UK that was characterized by Pyrolysis-Gas Chromatography-Mass Spectrometry (Py-GC-MS) at 700 oC. Pyrolysis products of the peat were then classified using the Vancampenhout classification into 6 compound classes - viz. aromatic and polyaromatic (Ar), phenols (Ph), lignin compounds (Lg), soil lipids (Lp), polysaccharide compounds (Ps) and N-compounds (N). There was no significant difference in the composition between the eroded and uneroded sites within the study area or between peats from different depths within each site. Nevertheless, there was a significant difference between sites in the proportions of Sphagnum that had contributed to the peat. Pyrolysis products of the peat were also classified into pedogenic (Pd) and aquagenic (Aq) OC – the mean percentage of Pd in both eroded and uneroded peats was 43.93 ± 4.30 % with the balance of the OC classified as Aq.Greenhouse gas (GHG) fluxes were quantified directly by in-situ continuous measurement of GHG was carried out at the E and U sites of the catchment using a GasClam: mean in-situ gas concentrations of CH4 (1.30 ± 0.04 % v/v (E), 0.59 ± 0.05 % v/v (U) and CO2 (8.83 ± 0.22 % v/v (E), 1.77 ± 0.03 % v/v (U)) were observed, with both the CH4 and CO2 concentrations apparently unrelated to atmospheric pressure and temperature changes. Laboratory measurements of ex-situ gas production - for both CH4 and CO2 this was higher for U site soils than for E site soils. At the U site, maximum production rates of both CH4 (46.11±1.47 mMol t-1 day-1) and CO2 (45.56 ± 10.19 mMol t-1 day-1) were observed for 0-50 cm depth in soils. Increased temperature did not affect gas production, whilst increased oxygen increased gas production. The CH4/CO2 ratios observed in-situ are not similar to those observed in the ex-situ laboratory experiments; suggest that some caution is advised in interpreting the latter. However, the maximum OC loss of 2.3 wt. % observed after 20 weeks of ex-situ incubation is nevertheless consistent with the long-term degradation noted by Bellamy et al (1985) from organic-rich UK soils. Indirect greenhouse gas (GHG) fluxes were quantified through the mass flux of suspended organic carbon (SsOC) drained from studied catchments. The SsOC was quantified by interpolating and rating methods. Unfiltered (UF) organic carbon (OC) fluxes in 2010 were calculated to be 8.86 t/km2/yr for the eroded sub-catchment and 6.74 t/km2/yr for the uneroded sub-catchment. All the rating relationships have a large amount of scatter. Both UF OC and <0.2 µm fraction OC are positively correlated with discharge at the eroded site, whilst there is no discernable relationship with discharge at the uneroded site. SsOC is dominated by Pd type OC (95.23 ± 10.20 % from E; 92.84 ± 5.38 % from U) far more so than in sources of the peats, suggesting slower oxidation of Pd (cf. Aq) OC.

Polycyclic aromatic hydrocarbons, derivates of polycyclic aromatic hydrocarbons, chromatography