Analytical Chemistry Commons^™

Coastal Watershed Monitoring And Management: Geomorphology, Geochemistry, And Hydrologic Modeling Of Los Peñasquitos Creek, Ca, Ravleen Khalsa-Basra

Theses

Rivers in semi-arid climates are directly influenced by local geographic and hydrologic conditions and impacted by modifications to hydrology via urbanization. Changes can influence erosion, morphology, habitat sustainability, and watershed health. In highly urbanized southern California coastal regions, these rare open spaces provide vital ecosystem services. Los Peñasquitos Creek in San Diego County is one such watershed. Using stream surveying and laboratory methods we quantified channel characteristics, grain size distribution, total metal concentration [M], organic carbon (%OC), and phosphate to longitudinally characterize the creek for improved management. Results identified three distinct reaches in the watershed (upper, middle, lower). Downstream, depth …

Otolith Microchemistry Reveals Low Habitat Connectivity Of California Killifish (Fundulus Parvipinnis) Across A Range Of Spatial Scales, Lisa Robison

Theses

As wetlands face continued fragmentation worldwide, an understanding of habitat connectivity and how fishes that rely on these environments is imperative to conduct effective marine management. Site fidelity and habitat connectivity are vital measures of the interdependence of fish populations living in neighboring marshes (or in regions of a single marsh).

Here, we examine the habitat connectivity, site fidelity, and movement of California killifish (Fundulus parvipinnis) within and among three estuaries in Southern California through otolith microelemental analysis. Assessing the site fidelity of estuarine fishes is important to determine the level of connectivity between spatially distinct populations within …

Evaluation Of Vaporization Enthalpies And Vapor Pressures Of Various Aroma And Pharmacologically Active Compounds By Correlation Gas Chromatography, Daniel Simmons

Theses

Scientists in the pharmaceutical, food, and aroma industries can benefit from reliable thermochemical data. Vaporization enthalpy and vapor pressure data are not available for all compounds. Furthermore, some literature data is conflicting. The goal of this work was to use a method called correlation gas chromatography (CGC) to generate reliable vaporization enthalpy data in instances where other experimental methods are not applicable. Vapor pressures of the targets were also calculated in cases where the required literature data on the standards used in this technique were available.

CGC involves making a standard cocktail that includes a mixture of standards and one …

Development Of Multi-Class Analytical Methods For Agrochemical Contaminants, Sarah Tuck

Theses

In this project, cost-effective multi-class analytical methods were developed to detect a range of antiparasitic, feed additive and pesticide substances in foodstuffs of animal origin. These substances have the potential to enter the food chain through their occurrence as residues either through the animals themselves or other routes e.g. contamination. To ensure the continued safety of food destined for human consumption regulatory control limits have been established for permitted levels of these residues in foods of animal origin. Despite these controls the continued monitoring of foodstuffs is necessary to ensure these limits are not breached and that substances are not …

The Development Of Liquid Chromatography Mass Spectrometry Methods For The Analysis Of Cyanobacterial Toxins In Environmental Freshwaters, Brian Anthony Dineen

Theses

Cyanobacteria, also known as blue-green algae, are a common component of many freshwater and marine ecosystems and have a potential to produce several different classes of biotoxins. The most common class of cyanobacterial toxins are the microcystins (MCs) and cylindrospermopsins (CYLs). MCs are cyclic heptapeptides that display potent hepatotoxicity and are tumour promoters. CYLs are alkaloids that are cytotoxic and can cause illness and display hepatotoxic effects in animals and humans. Worldwide, these toxins have caused fatal poisonings to animals, birds and fish. Several incidents of human intoxications have been reported and the presence of these toxins in environmental waters …

Investigation Of Pyrrolizidine Alkaloids In Foods Using Liquid Chromatography Mass Spectrometry, Caroline Griffin

Theses

Pyrrolizidine Alkaloids (PAs) are known plant toxins which can cause hepatic veno-occlusive disease (HVOD) in both humans and livestock when ingested. Although PAs are primarily known for their hepatotoxicity they also induce genotoxicity, carcinogenicity and pneumotoxicity. PAs are consumed through plants as food, for medicinal purposes, or as contaminants of agricultural crops. Aside from ingesting the plants directly PA exposure may occur through the consumption of honey produced by bees that visit PA-containing plants or by drinking milk produced by animals that have consumed PA-containing plants. Possible PA contamination in our food chain is a potential health risk.

To assess …

Novel Liquid Chromatography - Fourier Transform Mass Spectrometry (Ms) And Triple Quadrupole Ms Methods For The Determination Of Diarrhetic Shellfish Poisoning (Dsp) Toxins., Bébhine Carey

Theses

Harmful algal blooms (HABs) appear to be on the rise globally, which not only has a negative impact on the shellfish industry but can also cause human and animal intoxications. In order to advance our knowledge of HABs, specific and sensitive analytical methods are required to aid in monitoring shellfish and algal samples for biotoxins, harmful to consumers.

Investigation Of Drinking Water/Beverage Contaminants Within The Beverage Industry, Elizabeth Hobbs

Theses

The impact of water resource quality has influenced the community worldwide. It is an on-going target for water suppliers to produce suitable drinking water and the beverage industry to provide suitable water for the production of beverages. This diligence will ensure the consumer is provided with a product safe for consumption. The research and analytical techniques explored in this thesis may be of benefit to the beverage industry for the monitoring of inorganic contaminants present in water and carbonated soft drinks. The occurrence of certain contaminants in drinking water has become a major issue in the water industry in recent …

Development Of Mass Spectrometric Methods For The Analysis Of Serotonin And Related Compounds In Biological Matrices, Merisa Moriarty

Theses

Serotonin is a major neurotransmitter in the brain and affects various functions both in the brain and in the rest of the body. It has been linked to depression, migraines, and aggression, as well as many psychiatric disorders including schizophrenia, dementia and anorexia nervosa. It also has been associated with conditions like Alzheimer’s disease along with other neurotransmitters such as dopamine.

The aim of this research project is to develop various mass spectrometric methods for the analysis of serotonin, dopamine and similar indoles in both urine and serum matrices. This thesis provides extensive reviews detailing a general overview of serotonin …

Investigation Of Factors Influencing Trichloromethane Levels In Milk And Its Control., Siobhan Ryan

Theses

Trichloromethane (TCM) is an undesirable chemical residue that can develop in milk. While TCM levels in milk are not within ranges of public health concern, it is important that minimal levels are maintained in order to promote the marketing of Irish dairy products abroad. Germany has enacted strict regulations on TCM concentrations in foodstuffs with a recommended level of0.002 mg/kg and re-analyse those milks, subsequent to cause identification and provision of advice on reducing TCM levels in milk. Milk samples were analysed using Gas chromatography (GC) with electron capture detection. The GC method was adapted and a standard curve was …

Development, Validation And Application Of Uhplc-Ms/Ms Methods For The Detection Of Veterinary Drug Residues In Food Of Animal Origin, Michelle Whelan

Theses

Ultra high pressure liquid chromatography coupled to triple quadrupole mass spectrometry (UHPLC-MS/MS) technology was utilized for the development of analytical methods for the detection of veterinary drug residues in foods of animal origin. Initial work focused on the development of the mass spectrometry (MS) method for the detection of the analytes of interest and subsequent chromatographic separation. The MS method was optimised to detect both positively and negatively ionised analytes from different classes in a single injection in a 13 minute run time at μg kg^-1levels.

Sample preparation procedures were modified to extract the residues from muscle and …

High Resolution Hybrid Mass Spectrometry For The Determination Of Marine Biotoxins, Azaspiracids, And Their Biotransformation Products., Zuzana Skrabakova

Theses

Azaspiracids (AZAs), polyether marine toxins, are produced by marine microalgae and accumulate in filter-feeding bivalve molluscs, such as mussels, clams, oysters and scallops, while grazing on phytoplankton, from which they derive nutrition. Although being discovered quite recently, AZAs have caused several human intoxication events and thus became a problem for health authorities and shellfish industries. The rapid development of highly sensitive liquid chromatography multiple tandem mass spectrometry (LC-MS/MS, LC-MS") methods enabled the identification of numerous AZA analogues and added to the control of shellfish contamination. Tandem mass spectrometry techniques, while being highly selective and sensitive for determination of AZAs in …

Toxicodynamics And Biotransformation Of Azaspiracids Incorporating Liquid Chromatography-Tandem-Mass Spectrometry (Lc-Ms/Ms) Techniques., Daniel O'Driscoll

Theses

Azaspiracids (AZAs) are a family of lipophilic polyether marine biotoxins, that have caused a number of human intoxication incidents in Europe since 1995, which was the first incident reported following the consumption by consumers of intoxicated shellfish {Mytilus edulis). This class of phycotoxins has been responsible for extended closures of shellfisheries in various locations around Europe, where levels of AZAl-3 are regulated in shellfish. Since their discovery in 1995, AZAs have become the focus of extensive research, resulting in the discovery of numerous analogues. Only AZAl and AZA2 have been found in phytoplankton and all the other analogues are believed …

Application Of Liquid Chromatography - Tandem Mass Spectrometry For The Determination Of Veterinary Drug Residues In Food Of Animal Origin, Brian Kinsella

Theses

The QuEChERS (quick, easy, cheap, effective, rugged and safe) sample preparation approach was evaluated for the extraction of anthelmintic residues from bovine milk and tissues. Liquid chromatography coupled to tandem mass spectrom.etry (LC- MS/MS) was used for detection and quantification of residues, which included the benzimidazoles (BZs), macrocyclic lactones (MLS) and the generally overlooked flukicides.

Initial work focused on the optimisation of a QuEChERS method to effectively extract anthelmintic residues from milk and liver. The method involves the extraction of residues with acetonitrile (MeCN) in the presence of salts (MgS04 and NaCl) to induce phase separation. After shaking and centrifugation, …

Application Of Multiple Mass Spectrometric Techniques In The Isolation, Determination And Characterisation Of The Marine Toxins; Azaspiracid, Keith O'Callaghan

Theses

The Azaspiracids are a class of polyether marine biotoxins that present a significant health risk to consumers of shellfish. Since their discovery in the late 1990s several human intoxications have been reported, and traced to Irish shellfish farms resulting in closures or harvest rejections. As such incidents involving azaspiracid shellfish poisoning have a major socio-economic impact on communities that rely on shellfish farming revenues.

Recent evidence suggests that azaspiracid poisoning events may become more commonplace. With this increased risk the understanding of azaspiracids mode of action and biological targets becomes crucial. To support these endeavours effective analytical methods need to …

Elucidation Of The Mass Spectral Fragmentation Pathways Of Cyclic Hepatopeptides Microcystins, Paloma Muniz Ortea

Theses

The most frequently found cyanobacterial toxins in blooms from fresh and brackish waters are the cyclic peptide microcystins (MCs) and nodularin family. These toxins cause fatal poisonings of agricultural livestock, wild animals, birds and fish on a worldwide basis. The involvement of these toxins in human health problems has also been inferred in several countries and their presence in drinking water sources is of interest to the drinking water industry.

One of the biggest problems in the analysis of MCs is the lack of commercially available standards to be used for the identification and characterisation of these cyanobacterial toxins. One …

Exploring Marine Biotoxins Using Analytical Techniques Based On Mass Spectrometry, Mónica Fernández Amandi

Theses

The impact of phycotoxins on human and animal health is of important concern for worldwide authorities and the scientific community. Domoic acid (DA) is a neurotoxin produced by phytoplankton {Pseudonitzchia spp.). It enters the food chain through the consumption of shellfish that feed on toxic diatoms. DA has been responsible for several outbreaks affecting humans and animals all around the world. Yessotoxin (YTX) is produced by dinoflagellate species {Protoceratiuni reticulatum) which are globally distributed. Its toxicity is low when ingested orally. However, the co-extraction of YTX with diarrhetic shellfish poisoning (DSP) toxins, derives false positives when the mouse bioassay is …

The Synthesis And Characterisation Of Diiron And Triiron Carbonyl Cluster Compounds With Sulphur And Phosphine Ligands, Geraldine Gray

Theses

This work is primarily concerned with the synthesis and characterisation of di and triiron carbonyl cluster derivatives which contain sulphur and phosphine ligands.

The first chapter is a review of the literature of such complexes. Included are diiron carbonyl clusters which contain phosphine ligands, those which contain sulphur, and those that contain phosphine and sulphur ligands. Triiron carbonyl clusters which contain phosphine ligands, sulphur ligands and both are also discussed.

Chapter two describes the synthesis of compounds of the type [{Fe₂(SR)₂(CO)₅)₂Ph₂P (CH₂)_nPPh₂] (R = …

Development Of Electrochemical Sensors For Monitoring Glucose, Michael Nesbitt

Theses

The thesis focuses on evaluating calcium alginate as an immobilisation matrix for the oxidase enzyme glucose oxidase for the amperometric determination of glucose. The basic principles of enzymology and enzyme immobilisation is discussed followed by a review of a variety of first, second and third generation type enzyme electrodes. Amperometry as governed by the Cottrell equation and mass transfer models relating to amperometric electrodes are also considered.

Bovine serum albumin (BSA / GOx) enzyme electrode system was employed as a model to evaluate a calcium alginate immobilisation technique for glucose oxidase. The principal methods employed for enzyme immobilisation were:

• …

Analysis Of Phycotoxin And Mycotoxin, Contaminants In Foods, Using Liquid Chromatography - Mass Spectrometry Techniques, Ana Brana Magdalena

Theses

The impact of phycotoxins and mycotoxins on human and animal health are of important concern for worldwide authorities and the scientific community. Liquid chromatography-mass spectrometry (LC-MS) techniques have been developed, optimised and validated for the analysis of these toxins.

Phycotoxins are potentially toxic substances, which are produced by marine phytoplankton and which may accumulate in shellfish or finfish. Azaspiracid poisoning (AZP) is a recently discovered syndrome that has been implicated in several incidents of human intoxications. A study was undertaken to examine the distribution of azaspiracids (AZA) in scallops {Pecten maximiis) and mussels {Mytiliis edulis). Domoic acid (DA) is an …

Development Of Amperometric Enzyme Electrodes For Glucose And Hypoxanthine., Eilish Broderick

Theses

This thesis is concerned with the immobilisation of enzymes on electrosynthesised poly (o- phenylenediamine) membranes for use on amperometric electrodes. The thesis opens with a discussion of the basic principles of enzymology and a review of a diverse range of biosensors, followed by a consideration of amperometry as governed by the Cottrell equation.

Glucose oxidase and horseradish peroxidase were co-immobilised in poly (o-phenylenediamine) on platinum electrodes at + 0.6 V versus Ag/AgCl. Using this approach the enzymes are entrapped in a strongly adherent, highly reproducible thin membrane, of thickness approximately 10 nm. This one-step procedure produces a glucose sensor with …

New Polyether Toxins From Shellfish And Marine Phytoplankton: Isolation Studies And Development Of Analytical Methods, Alan G. Bishop

Theses

There are three classes of polyether toxins responsible for Diarrhetic Shellfish Poisoning (DSP) world-wide. The causative toxins are okadaic acid (OA) and derivatives (DTXs), pectenotoxins (PTXs) and yessotoxins (YTXs). The origin of these toxins are phytoplankton from Dinophysis or Prorocentrum spp. OA has been demonstrated for most outbreaks in Europe and more recently a new isomer DTX-2 has been reported in Ireland.

Marine phytoplankton biomass samples consisting predominantly of Dinophysis acuta, were acquired using a large double plankton net from waters off the South-west coast of Ireland. Analysis of unialgal samples using high performance liquid chromatography (HPLC) with fluorescence and …

Acidic Marine Biotoxins Implicated In Diarrhetic Shellfish Poisoning, Eoin P. Carmody

Theses

An okadaic acid (OA) etiology has been demonstrated for most outbreaks of diarrhetic shellfish poisoning (DSP) in Europe, An isomer of OA, dinophysistoxin-2 (DTX-2), has recently been found in Irish waters and, in 1991 and 1994, was the major toxin during prolonged infestations in cultivated mussels (Mytilus edulis) along the south-west coast of Ireland.

The OA class of DSP toxins have been analysed by HPLC using modified versions of three established fluorescent derivatisation methods. A ‘dual tag’ method for the confirmation of specific toxins has also been developed.

Survey work has been carried out over the past four years on …

The Analysis And Isolation Of Diarrhetic Shellfish Poisoning Toxins, Seán S. Kelly

Theses

This research was initiated to examine the Diarrhetic Shellfish Poisoning (DSP) toxin profiles in mussels (Mytilus edulis) in south-west Ireland. Extensive sampling and testing of shellfish was conducted during the toxic periods of 1991 to 1994. This was the most comprehensive study ever undertaken of toxin profiles in shellfish from a single cultivation area.

A new toxin named dinophysistoxin-2 (DTX-2), which is an isomer of okadaic acid (OA), was the major toxin during prolonged DSP episodes. This toxicity in shellfish occuired soon after high cell counts of Dinophysis acuta were observed. As well as seasonal variability in toxin levels, substantial …