Characterisation of atmospheric single particles in industrial and regional background environments using aerosol time of flight mass spectrometry

The composition of atmospheric particles is an important factor in determining their impact on climate and health. In this study, an aerosol time-of-flight mass spectrometer (ATOFMS) was used to measure the chemical composition of ambient single particles at two contrasting locations – an industrial site in Dunkirk, France and a regional background site in Corsica. The ATOFMS data were combined with meteorological information and other particle measurements to determine the various sources of the particles observed at the sites. The particle classes detected in Dunkirk included carbonaceous species from fossil fuel combustion and biomass burning, metal-containing types from local industries and seasalt. Highest particle number concentrations and mass concentrations of PM2.5, black carbon, organics, nitrate, ammonium and several metallic species (Fe, Mn, Pb, Zn) were found during periods heavily influenced by local industry. Particles from a ferromanganese alloy manufacturing facility were identified by comparing ambient ATOFMS data with single particle mass spectra from industrial chimney filters and ores. Particles from a steelworks were identified based on comparison of the ambient data with previous studies. Based on these comparisons, the steelworks was identified as the dominant emitter of Fe-rich particles, while the ferromanganese alloy facility emitted Mn-rich particles. In Corsica, regional transport of carbonaceous particles from biomass burning and fossil fuel combustion was identified as the major source of particles in the Mediterranean background aerosol. Throughout the campaign the site was influenced by air masses altering the composition of particles detected. During North Atlantic air masses the site was heavily influenced by fresh sea salt. Regional stagnation was the most common type of air mass regime throughout the campaign and resulted in the accumulation of carbonaceous particles during certain periods. Mass concentrations were estimated for ATOFMS particle classes, and good agreement was found between the major carbonaceous classes and other quantitative measurements. Overall the results of this work serve to highlight the excellent ability of the ATOFMS technique in providing source-specific composition and mixing state information on atmospheric particles at high time resolution.

The application of next generation sequencing to profile microbe related cheese quality defects

High throughput next generation sequencing, together with advanced molecular methods, has considerably enhanced the field of food microbiology. By overcoming biases associated with culture dependant approaches, it has become possible to achieve novel insights into the nature of food-borne microbial communities. In this thesis, several different sequencing-based approaches were applied with a view to better understanding microbe associated quality defects in cheese. Initially, a literature review provides an overview of microbe-associated cheese quality defects as well as molecular methods for profiling complex microbial communities. Following this, 16S rRNA sequencing revealed temporal and spatial differences in microbial composition due to the time during the production day that specific commercial cheeses were manufactured. A novel Ion PGM sequencing approach, focusing on decarboxylase genes rather than 16S rRNA genes, was then successfully employed to profile the biogenic amine producing cohort of a series of artisanal cheeses. Investigations into the phenomenon of cheese pinking formed the basis of a joint 16S rRNA and whole genome shotgun sequencing approach, leading to the identification of Thermus species and, more specifically, the pathway involved in production of lycopene, a red coloured carotenoid. Finally, using a more traditional approach, the effect of addition of a facultatively heterofermentative Lactobacillus (Lactobacillus casei) to a Swiss-type cheese, in which starter activity was compromised, was investigated from the perspective of its ability to promote gas defects and irregular eye formation. X-ray computed tomography was used to visualise, using a non-destructive method, the consequences of the undesirable gas formation that resulted. Ultimately this thesis has demonstrated that the application of molecular techniques, such as next generation sequencing, can provide a detailed insight into defect-causing microbial populations present and thereby may underpin approaches to optimise the quality and consistency of a wide variety of cheeses.

Manganese nodule geochemistry from the Challenger Expedition

C. W. Gümbel received nodules from J. Murray which were collected at a depth of 2740 fathoms, between Japan and the Sandwich Islands, by the "Challenger" Expedition. They were either round or long in shape, with a dull, dirty-brown coloured surface, and enclosed fragments of pumice-stone, and more rarely teeth of sharks or fragments of mussels. They were analysed by A. Schwager.

Bacteriological investigations in the Persian Gulf

While the R.V. "Meteor" was in the eastern Persian Gulf, during the time between March 31 and April 14, 1965, bacteriological investigations of the water and sediment were performed. The content of saprophytic bacteria in the water decreases from the coasts outward to the middle of the gulf. This shows a good correlation with the turbidity values. In a sediment core from the southern part of the gulf, the bacterial counts in all the horizonts were much higher than those from the northern part of the Persian Gulf. This agrees with the findings of the geologists, according to which the proportion of carbon compounds in the sediments decreases from south to north. Luminous bacteria were found in many samples of water. Their proportion of the saprophytic flora becomes less from south to north. Most of the water samples also contained pigmented bacteria. On freshwater medium, relatively few bacteria were able to develop. The proportion of these non-halophilic forms amounted up to 7 % (average about 1 %) of the total saprophytic count, in 22 samples examined. In this group the pigmented forms played a very large role. A comparison of the distribution of saprophytic bacteria in the eastern Persian Gulf with that in other inland seas such as the North Sea and the Baltic Sea shows, that the saprophytic counts in the subtropical Persian Gulf (arid region) lie clearly below those in corresponding sea areas of the temperate zones (humid region). This is to be attributed above all to the greater flow of organic nutrients into the latter.

Annotated record of the detailed examination of Mn deposits from the H.M.S. Penguin expedition to the Coral Sea

The analyses of the samples from the Balfour Shoal show that these deposits contain a very large quantity of carbonate of lime, ranging from 88.7 per cent, on the summit to 71.9 per cent, in the deeper water at the base of the cone. The decrease in the quantity of carbonate of lime with increase of depth is not quite regular; still, a general fall in the percentage of lime is clearly indicated from shallower to deeper water. As might be expected in such a circumscribed area, there is a great uniformity both in the chemical composition and relative abundance of the organic and inorganic constituents of the deposits. In all cases the carbonate of lime is almost wholly made up of the dead shells which have fallen from the surface waters - belonging to Plankton organisms such as Pteropods, Heteropods, pelagic Foraminifera and coccoliths. The calcareous shells were in very many cases discoloured brown or black by depositions of the peroxide of manganese. On the north-east steep side of the Balfour Shoal there were indications that depositions of manganese peroxide were more abundant than elsewhere. In 1645 fathoms, there was an angular fragment of a mottled yellowish jasper coated with manganese peroxide, and in 1570 fathoms there were three characteristic spherical black manganese nodules from one-half to three-fourths of an inch in diameter, quite similar to those procured by the Challenger in many areas of the Pacific and Atlantic. In one of these nodules the nucleus was a sub-angular fragment of a light-coloured augite-granophyre.

Landfill Leachate Toxicity to Oncorhynchus mykiss (Rainbow Trout) at the Merrick Landfill

At the Merrick Landfill, located outside of North Bay (Ontario, CA), an investigation into the potential for an environmental impact to the Little Sturgeon River as a result of landfill leachate discharge was undertaken using toxicity testing using 96 hour acute lethality on Oncorhynchus mykiss (Rainbow Trout). Landfill leachate may present a risk to receiving environments as it is comprised of an array of chemicals including organics, ammonia, and metals. Testing was conducted in three phases, firstly testing was completed on site throughout an existing natural attenuation zone where the presence of several groundwater seeps down gradient of the site had been identified to determine the effectiveness of the existing leachate control features at reducing the environmental risks. These tests indicated that the existing capture strategies were largely effective at reducing toxicity risks to the receiving environment. Testing was also completed on two pilot-scale hybrid-passive treatment systems to determine their effectiveness for leachate treatment. Summer performance of a constructed gravel wetland system was also shown to be effective at reducing the toxicity of the landfill leachate at the site. Lastly in order to support evaluation of leachate treatment requirements, a toxicity identification evaluation (TIE) was performed to determine the principle cause of toxicity within the leachate. Based on water chemistry analyses of samples collected at various locations at the site, the TIE identified ammonia toxicity as the primary source of toxicity in the leachate, with a secondary focus on metal toxicity.

Observed bodies generate object-based spatial codes

Contemporary studies of spatial and social cognition frequently use human figures as stimuli. The interpretation of such studies may be complicated by spatial compatibility effects that emerge when researchers employ spatial responses, and participants spontaneously code spatial relationships about an observed body. Yet, the nature of these spatial codes – whether they are location- or object-based, and coded from the perspective of the observer or the figure – has not been determined. Here, we investigated this issue by exploring spatial compatibility effects arising for objects held by a visually presented whole-bodied schematic human figure. In three experiments, participants responded to the colour of the object held in the figure’s left or right hand, using left or right key presses. Left-right compatibility effects were found relative to the participant’s egocentric perspective, rather than the figure’s. These effects occurred even when the figure was rotated by 90 degrees to the left or to the right, and the coloured objects were aligned with the participant’s midline. These findings are consistent with spontaneous spatial coding from the participant’s perspective and relative to the normal upright orientation of the body. This evidence for object-based spatial coding implies that the domain general cognitive mechanisms that result in spatial compatibility effects may contribute to certain spatial perspective-taking and social cognition phenomena.

Multifunctional anthraquinone-based sensors: UV, O2and time

An anthraquinone dye, Remazol brilliant blue R, RBBR, is used to create an indicator which can function as: (i) a UV dosimeter, (ii) an O2 indicator and (iii) a ‘Consume within’ indicator, CWI, for fresh, refrigerated foods. The dye is encapsulated in an ink containing a polymer, glycerol and a UV-activated semiconductor photocatalyst, titanium dioxide. When cast as a film, the dye is readily reduced by the TiO2 photocatalyst nanoparticles, thereby changing the colour of the film from blue to yellow, via a transitional green colour. The RBBR indicator is appropriately formulated, and covered with a film of Sellotape, which acts as an O2 barrier, so as to act as a sunburn warning indicator for people with skin type II. In the absence of the layer of Sellotape the RBBR indicator is used as an, albeit slow, sensor for measuring ambient levels of O2. Finally, by keeping the Sellotape layer, a UV-activated, yellow-coloured, RBBR indicator film is found to take ca. 42 h at 5 °C in ambient air to attain a green colour, and, on this basis, it is demonstrated as a possible CWI for refrigerated fresh foods.

Investigation of the chemical origin and evidential value of differences in the SERS spectra of blue gel inks

Highly swellable polymer films doped with Ag nanoparticle aggregates (poly-SERS films) have been used to record very high signal:noise ratio, reproducible surface-enhanced (resonance) Raman (SER(R)S) spectra of in situ dried ink lines and their constituent dyes using both 633 and 785 nm excitation. These allowed the chemical origins of differences in the SERRS spectra of different inks to be determined. Initial investigation of pure samples of the 10 most common blue dyes showed that the dyes which had very similar chemical structures such as Patent Blue V and Patent Blue VF (which differ only by a single OH group) gave SERRS spectra in which the only indications that the dye structure had been changed were small differences in peak positions or relative intensities of the bands. SERRS studies of 13 gel pen inks were consistent with this observation. In some cases inks from different types of pens could be distinguished even though they were dominated by a single dye such as Victoria Blue B (Zebra Surari) or Victoria Blue BO (Pilot Acroball) because their predominant dye did not appear in other inks. Conversely, identical spectra were also recorded from different types of pens (Pilot G7, Zebra Z-grip) because they all had the same dominant Brilliant Blue G dye. Finally, some of the inks contained mixtures of dyes which could be separated by TLC and removed from the plate before being analysed with the same poly-SERS films. For example, the Pentel EnerGel ink pen was found to give TLC spots corresponding to Erioglaucine and Brilliant Blue G. Overall, this study has shown that the spectral differences between different inks which are based on chemically similar, but nonetheless distinct dyes, are extremely small, so very close matches between SERRS spectra are required for confident identification. Poly-SERS substrates can routinely provide the very stringent reproducibility and sensitivity levels required. This, coupled with the awareness of the reasons underlying the observed differences between similarly coloured inks allows a more confident assessment of the evidential value of inks SERS and should underpin adoption of this approach as a routine method for the forensic examination of inks.

A Non-catalytic Deep Desulphurization Process using Hydrodynamic Cavitation

A novel approach is developed for desulphurization of fuels or organics without use of catalyst. In this process, organic and aqueous phases are mixed in a predefined manner under ambient conditions and passed through a cavitating device. Vapor cavities formed in the cavitating device are then collapsed which generate (in-situ) oxidizing species which react with the sulphur moiety resulting in the removal of sulphur from the organic phase. In this work, vortex diode was used as a cavitating device. Three organic solvents (n-octane, toluene and n-octanol) containing known amount of a model sulphur compound (thiophene) up to initial concentrations of 500 ppm were used to verify the proposed method. A very high removal of sulphur content to the extent of 100% was demonstrated. The nature of organic phase and the ratio of aqueous to organic phase were found to be the most important process parameters. The results were also verified and substantiated using commercial diesel as a solvent. The developed process has great potential for deep of various organics, in general, and for transportation fuels, in particular.

Congruences in modular, Jacobi, Siegel, and mock modular forms with applications

We study congruences in the coefficients of modular and other automorphic forms. Ramanujan famously found congruences for the partition function like p(5n+4) = 0 mod 5. For a wide class of modular forms, we classify the primes for which there can be analogous congruences in the coefficients of the Fourier expansion. We have several applications. We describe the Ramanujan congruences in the counting functions for overparitions, overpartition pairs, crank differences, and Andrews' two-coloured generalized Frobenius partitions. We also study Ramanujan congruences in the Fourier coefficients of certain ratios of Eisenstein series. We also determine the exact number of holomorphic modular forms with Ramanujan congruences when the weight is large enough. In a chapter based on joint work with Olav Richter, we study Ramanujan congruences in the coefficients of Jacobi forms and Siegel modular forms of degree two. Finally, the last chapter contains a completely unrelated result about harmonic weak Maass forms.

Ultrasound-assisted electrochemical treatment of wastewaters containing organic pollutants by using novel Ti/Ta2O5-SnO2 electrodes

Advanced oxidation processes (AOPs) are modern methods using reactive hydroxyl radicals for the mineralization of organic pollutants into simple inorganic compounds, such as CO2 and H2O. Among AOPs electrochemical oxidation (EO) is a method suitable for coloured and turbid wastewaters. The degradation of pollutants occurs on electrocatalytic electrodes. The majority of electrodes contain in their structure either expensive materials (diamond and Pt-group metals) or are toxic for the environment compounds (Sb or Pb). One of the main disadvantages of electrochemical method is the polarization and contamination of electrodes due to the deposition of reaction products on their surface, which results in diminishing of the process efficiency. Ultrasound combined with the electrochemical degradation process eliminates electrode contamination because of the continuous mechanical cleaning effect produced by the formation and collapse of acoustic cavitation bubbles near to the electrode surface. Moreover, high frequency ultrasound generates hydroxyl radicals at water sonolysis. Ultrasound-assisted EO is a non-selective method for oxidation of different organic compounds with high degradation efficiencies. The aim of this research was to develop novel sustainable and cost-effective electrodes working as electrocatalysts and test their activity in electrocatalytic oxidation of organic compounds such as dyes and organic acids. Moreover, the goal of the research was to enhance the efficiency of electrocatalytic degradation processes by assisting it with ultrasound in order to eliminate the main drawbacks of a single electrochemical oxidation such as electrodes polarization and passivation. Novel Ti/Ta2O5-SnO2 electrodes were developed and found to be electrocatalytically active towards water (with 5% Ta content, 10 oxide film layers) and organic compounds oxidation (with 7.5% Ta content, 8 oxide film layers) and therefore these electrodes can be applicable in both environmental and energy fields. The synergetic effect of combined electrolysis and sonication was shown while conducting sonoelectrochemical (EO/US) degradation of methylene blue (MB) and formic acid (FA). Complete degradation of MB and FA was achieved after 45 and 120 min of EO/US process respectively in neutral media. Mineralization efficiency of FA over 95% was obtained after 2 h of degradation using high frequency ultrasound (381, 863, 1176 kHz) combined with 9.1 mA/cm2 current density. EO/US degradation of MB provided over 75% mineralization in 8 h. High degradation kinetic rates and mineralization efficiencies of model pollutants obtained in EO/US experiments provide the preconditions for further extrapolation of this treatment method to pilot scale studies with industrial wastewaters.

Transient Blue Skin: Pseudochromhidrosis

Objectives: Pseudochromhidrosis is a rare condition where colours due to chromogenic microbial products or extrinsic chemicals are excreted with sweat. Chromhidrosis is the production of coloured sweat from apocrine or eccrine sweat glands. The aim of this case report is to illustrate all the steps involved in the diagnosis of pseudochromhidrosis. Materials and methods: A 17-year-old patient with pseudochromhidrosis is presented. Results: Clinical features of the patient were consistent with pseudochromhidrosis. Conclusions: The distinction between chromhidrosis and pseudochromhidrosis can be made based on a detailed history, skin biopsy and empiric treatment

Joseph McKeen and the soul of Bowdoin College: an analysis of the chapel sermons of Rev. Joseph McKeen, first president of Bowdoin College, as they relate to his call to serve the common good

The Reverend Joseph McKeen (1757-1807) was the first president of Bowdoin College, Brunswick, Maine, USA, (founded 1794). McKeen is famous for his inaugural address in which he calls students to serve the common good. His view of common good is a deeply theological view, coloured by the theological era in which he lived and worked. This study examines the idea of common in the light of McKeen’s college sermons, taking note of the following subjects: Scottish Common Sense Realism; The Nature of True Virtue; The Controversy with Unitarianism; and Science and Mathematics. McKeen’s view of common good is not simply a political view. He is not merely a republican, expressing his views on the future of the republic in a classical political way. He is also, indeed primarily, a pastor and theologian.

Performances of dead-end ultrafiltration of seawater: from the filtration and backwash efficiencies to the membrane fouling mechanisms

The present work investigates the fouling mechanisms of PVDF hollow fibre membrane (0.03 μm) during the dead end ultrafiltration at a fixed permeate flux (outside to inside configuration) of complex synthetic seawater composed by humic acids, alginic acids, inorganic particles and numerous salts at high concentrations. Short term ultrafiltration experiments at 100 L.h-1.m-2 show that the optimal specific filtered volume seems to be equal to 50 L.m-2. A residual fouling resistance equal to 2.1010 m-1 is added after each cycle of filtration during 8h of ultrafiltration at 100 L.h-1.m-2 and 50 L.m-2. Most of the fouling is reversible (80%). Organics are barely (15% of humic acids) retained by the membrane. Backwash efficiency drops during operation which induces less organics into backwash waters. Humic acids could preferentially accumulate on the membrane early in the ultrafiltration and alginic acids after the build-up of a fouling pre-layer. Colloids and particulates could accumulate inside a heterogeneous fouling layer and/or the concentrate compartment of the membrane module before being more largely recovered inside backwash waters.