Development of oil spill detection techniques for satellite optical sensors and their application to monitor oil spill discharge in Mediterranean sea

Satellite remote sensing has proved to be an effective support in timely detection and monitoring of marine oil pollution, mainly due to illegal ship discharges. In this context, we have developed a new methodology and technique for optical oil spill detection, which make use of MODIS L2 and MERIS L1B satellite top of atmosphere (TOA) reflectance imagery, for the first time in a highly automated way. The main idea was combining wide swaths and short revisit times of optical sensors with SAR observations, generally used in oil spill monitoring. This arises from the necessity to overcome the SAR reduced coverage and long revisit time of the monitoring area. This can be done now, given the MODIS and MERIS higher spatial resolution with respect to older sensors (250-300 m vs. 1 km), which consents the identification of smaller spills deriving from illicit discharge at sea. The procedure to obtain identifiable spills in optical reflectance images involves removal of oceanic and atmospheric natural variability, in order to enhance oil-water contrast; image clustering, which purpose is to segment the oil spill eventually presents in the image; finally, the application of a set of criteria for the elimination of those features which look like spills (look-alikes). The final result is a classification of oil spill candidate regions by means of a score based on the above criteria.

Fiber-Optic Technologies for Wireline and Wireless In-building Networks

This doctoral dissertation aims to establish fiber-optic technologies overcoming the limiting issues of data communications in indoor environments. Specific applications are broadband mobile distribution in different in-building scenarios and high-speed digital transmission over short-range wired optical systems. Two key enabling technologies are considered: Radio over Fiber (RoF) techniques over standard silica fibers for distributed antenna systems (DAS) and plastic optical fibers (POFs) for short-range communications. Hence, the objectives and achievements of this thesis are related to the application of RoF and POF technologies in different in-building scenarios. On one hand, a theoretical and experimental analysis combined with demonstration activities has been performed on cost-effective RoF systems. An extensive modeling on modal noise impact both on linear and non-linear characteristics of RoF link over silica multimode fiber has been performed to achieve link design rules for an optimum choice of the transmitter, receiver and launching technique. A successful transmission of Long Term Evolution (LTE) mobile signals on the resulting optimized RoF system over silica multimode fiber employing a Fabry-Perot LD, central launch technique and a photodiode with a built-in ball lens was demonstrated up to 525m with performances well compliant with standard requirements. On the other hand, digital signal processing techniques to overcome the bandwidth limitation of POF have been investigated. An uncoded net bit-rate of 5.15Gbit/s was obtained on a 50m long POF link employing an eye-safe transmitter, a silicon photodiode, and DMT modulation with bit and power loading algorithm. With the insertion of 3x2N quadrature amplitude modulation constellation formats, an uncoded net-bit-rate of 5.4Gbit/s was obtained on a 50 m long POF link employing an eye-safe transmitter and a silicon avalanche photodiode. Moreover, simultaneous transmission of baseband 2Gbit/s with DMT and 200Mbit/s with an ultra-wideband radio signal has been validated over a 50m long POF link.

New platforms for optical biosensing

Physicochemical experimental techniques combined with the specificity of a biological recognition system have resulted in a variety of new analytical devices known as biosensors. Biosensors are under intensive development worldwide because they have many potential applications, e.g. in the fields of clinical diagnostics, food analysis, and environmental monitoring. Much effort is spent on the development of highly sensitive sensor platforms to study interactions on the molecular scale. In the first part, this thesis focuses on exploiting the biosensing application of nanoporous gold (NPG) membranes. NPG with randomly distributed nanopores (pore sizes less than 50 nm) will be discussed here. The NPG membrane shows unique plasmonic features, i.e. it supports both propagating and localized surface plasmon resonance modes (p SPR and l-SPR, respectively), both offering sensitive probing of the local refractive index variation on/in NPG. Surface refractive index sensors have an inherent advantage over fluorescence optical biosensors that require a chromophoric group or other luminescence label to transduce the binding event. In the second part, gold/silica composite inverse opals with macroporous structures were investigated with bio- or chemical sensing applications in mind. These samples combined the advantages of a larger available gold surface area with a regular and highly ordered grating structure. The signal of the plasmon was less noisy in these ordered substrate structures compared to the random pore structures of the NPG samples. In the third part of the thesis, surface plasmon resonance (SPR) spectroscopy was applied to probe the protein-protein interaction of the calcium binding protein centrin with the heterotrimeric G-protein transducin on a newly designed sensor platform. SPR spectroscopy was intended to elucidate how the binding of centrin to transducin is regulated towards understanding centrin functions in photoreceptor cells.

Surface-plasmon optical and electrochemical characterization of biofunctional surface architectures

The development and characterization of biomolecule sensor formats based on the optical technique Surface Plasmon Resonance (SPR) Spectroscopy and electrochemical methods were investigated. The study can be divided into two parts of different scope. In the first part new novel detection schemes for labeled targets were developed on the basis of the investigations in Surface-plamon Field Enhanced Spectroscopy (SPFS). The first one is SPR fluorescence imaging formats, Surface-plamon Field Enhanced Fluorescence Microscopy (SPFM). Patterned self assembled monolayers (SAMs) were prepared and used to direct the spatial distribution of biomolecules immobilized on surfaces. Here the patterned monolayers would serve as molecular templates to secure different biomolecules to known locations on a surface. The binding processed of labeled target biomolecules from solution to sensor surface were visually and kinetically recorded by the fluorescence microscope, in which fluorescence was excited by the evanescent field of propagating plasmon surface polaritons. The second format which also originates from SPFS technique, Surface-plamon Field Enhanced Fluorescence Spectrometry (SPFSm), concerns the coupling of a fluorometry to normal SPR setup. A spectrograph mounted in place of photomultiplier or microscope can provide the information of fluorescence spectrum as well as fluorescence intensity. This study also firstly demonstrated the analytical combination of surface plasmon enhanced fluorescence detection with analyte tagged by semiconducting nano- crystals (QDs). Electrochemically addressable fabrication of DNA biosensor arrays in aqueous environment was also developed. An electrochemical method was introduced for the directed in-situ assembly of various specific oligonucleotide catcher probes onto different sensing elements of a multi-electrode array in the aqueous environment of a flow cell. Surface plasmon microscopy (SPM) is utilized for the on-line recording of the various functionalization steps. Hybridization reactions between targets from solution to the different surface-bound complementary probes are monitored by surface-plasmon field-enhanced fluorescence microscopy (SPFM) using targets that are either labeled with organic dyes or with semiconducting quantum dots for color-multiplexing. This study provides a new approach for the fabrication of (small) DNA arrays and the recording and quantitative evaluation of parallel hybridization reactions. In the second part of this work, the ideas of combining the SP optical and electrochemical characterization were extended to tethered bilayer lipid membrane (tBLM) format. Tethered bilayer lipid membranes provide a versatile model platform for the study of many membrane related processes. The thiolipids were firstly self-assembled on ultraflat gold substrates. Fusion of the monolayers with small unilamellar vesicles (SUVs) formed the distal layer and the membranes thus obtained have the sealing properties comparable to those of natural membranes. The fusion could be monitored optically by SPR as an increase in reflectivity (thickness) upon formation of the outer leaflet of the bilayer. With EIS, a drop in capacitance and a steady increase in resistance could be observed leading to a tightly sealing membrane with low leakage currents. The assembly of tBLMs and the subsequent incorporation of membrane proteins were investigated with respect to their potential use as a biosensing system. In the case of valinomycin the potassium transport mediated by the ion carrier could be shown by a decrease in resistance upon increasing potassium concentration. Potential mediation of membrane pores could be shown for the ion channel forming peptide alamethicin (Alm). It was shown that at high positive dc bias (cis negative) Alm channels stay at relatively low conductance levels and show higher permeability to potassium than to tetramethylammonium. The addition of inhibitor amiloride can partially block the Alm channels and results in increase of membrane resistance. tBLMs are robust and versatile model membrane architectures that can mimic certain properties of biological membranes. tBLMs with incorporated lipopolysaccharide (LPS) and lipid A mimicking bacteria membranes were used to probe the interactions of antibodies against LPS and to investigate the binding and incorporation of the small antimicrobial peptide V4. The influence of membrane composition and charge on the behavior of V4 was also probed. This study displays the possibility of using tBLM platform to record and valuate the efficiency or potency of numerous synthesized antimicrobial peptides as potential drug candidates.

Noble-metal nanoparticles produced with colloidal lithography: fabrication, optical properties and applications

In this work, metal nanoparticles produced by nanosphere lithography were studied in terms of their optical properties (in connection to their plasmon resonances), their potential application in sensing platforms - for thin layer sensing and bio-recognition events -, and for a particular case (the nanocrescents), for enhanced spectroscopy studies. The general preparation procedures introduced early in 2005 by Shumaker-Parry et al. to produce metallic nanocrescents were extended to give rise to more complex (isolated) structures, and also, by combining colloidal monolayer fabrication and plasma etching techniques, to arrays of them. The fabrication methods presented in this work were extended not only to new shapes or arrangements of particles, but included also a targeted surface tailoring of the substrates and the structures, using different thiol and silane compounds as linkers for further attachment of, i.e. polyelectrolyte layers, which allow for a controlled tailoring of their nanoenvironment. The optical properties of the nanocrescents were studied with conventional transmission spectroscopy; a simple multipole model was adapted to explain their behaviour qualitatively. In terms of applications, the results on thin film sensing using these particles show that the crescents present an interesting mode-dependent sensitivity and spatial extension. Parallel to this, the penetrations depths were modeled with two simplified schemes, obtaining good agreement with theory. The multiple modes of the particles with their characteristic decay lengths and sensitivities represent a major improvement for particle-sensing platforms compared to previous single resonance systems. The nanocrescents were also used to alter the emission properties of fluorophores placed close to them. In this work, green emitting dyes were placed at controlled distances from the structures and excited using a pulsed laser emitting in the near infrared. The fluorescence signal obtained in this manner should be connected to a two-photon processes triggered by these structures; obtaining first insight into plasmon-mediated enhancement phenomena. An even simpler and faster approach to produce plasmonic structures than that for the crescents was tested. Metallic nanodiscs and nanoellipses were produced by means of nanosphere lithography, extending a procedure reported in the literature to new shapes and optical properties. The optical properties of these particles were characterized by extinction spectroscopy and compared to results from the literature. Their major advantage is that they present a polarization-dependent response, like the nanocrescents, but are much simpler to fabricate, and the resonances can be tailored in the visible with relative ease. The sensing capabilities of the metallic nanodiscs were explored in the same manner as for the nanocrescents, meaning their response to thin layers and to bio-recognition events on their surface. The sensitivity of these nanostructures to thin films proved to be lower than that of the crescents, though in the same order of magnitude. Experimental information about the near field extension for the Au nanodiscs of different sizes was also extracted from these measurements. Further resonance-tailoring approaches based on electrochemical deposition of metals on the nanodiscs were explored, as a means of modifying plasmon resonances by changing surface properties of the nanoparticles. First results on these experiments would indicate that the deposition of Ag on Au on a submonolayer coverage level can lead to important blue-shifts in the resonances, which would open a simple way to tailor resonances by changing material properties in a local manner.

Bottle microresonators for applications in quantum optics and all-optical signal processing

This thesis reports on the experimental realization, characterization and application of a novel microresonator design. The so-called “bottle microresonator” sustains whispering-gallery modes in which light fields are confined near the surface of the micron-sized silica structure by continuous total internal reflection. While whispering-gallery mode resonators in general exhibit outstanding properties in terms of both temporal and spatial confinement of light fields, their monolithic design makes tuning of their resonance frequency difficult. This impedes their use, e.g., in cavity quantum electrodynamics (CQED) experiments, which investigate the interaction of single quantum mechanical emitters of predetermined resonance frequency with a cavity mode. In contrast, the highly prolate shape of the bottle microresonators gives rise to a customizable mode structure, enabling full tunability. The thesis is organized as follows: In chapter I, I give a brief overview of different types of optical microresonators. Important quantities, such as the quality factor Q and the mode volume V, which characterize the temporal and spatial confinement of the light field are introduced. In chapter II, a wave equation calculation of the modes of a bottle microresonator is presented. The intensity distribution of different bottle modes is derived and their mode volume is calculated. A brief description of light propagation in ultra-thin optical fibers, which are used to couple light into and out of bottle modes, is given as well. The chapter concludes with a presentation of the fabrication techniques of both structures. Chapter III presents experimental results on highly efficient, nearly lossless coupling of light into bottle modes as well as their spatial and spectral characterization. Ultra-high intrinsic quality factors exceeding 360 million as well as full tunability are demonstrated. In chapter IV, the bottle microresonator in add-drop configuration, i.e., with two ultra-thin fibers coupled to one bottle mode, is discussed. The highly efficient, nearly lossless coupling characteristics of each fiber combined with the resonator's high intrinsic quality factor, enable resonant power transfers between both fibers with efficiencies exceeding 90%. Moreover, the favorable ratio of absorption and the nonlinear refractive index of silica yields optical Kerr bistability at record low powers on the order of 50 µW. Combined with the add-drop configuration, this allows one to route optical signals between the outputs of both ultra-thin fibers, simply by varying the input power, thereby enabling applications in all-optical signal processing. Finally, in chapter V, I discuss the potential of the bottle microresonator for CQED experiments with single atoms. Its Q/V-ratio, which determines the ratio of the atom-cavity coupling rate to the dissipative rates of the subsystems, aligns with the values obtained for state-of-the-art CQED microresonators. In combination with its full tunability and the possibility of highly efficient light transfer to and from the bottle mode, this makes the bottle microresonator a unique tool for quantum optics applications.

Electrochemical surface modification of Single walled carbon nanotubes and graphene-based electrodes for (bio)sensing applications

Sensors are devices that have shown widespread use, from the detection of gas molecules to the tracking of chemical signals in biological cells. Single walled carbon nanotube (SWCNT) and graphene based electrodes have demonstrated to be an excellent material for the development of electrochemical biosensors as they display remarkable electronic properties and the ability to act as individual nanoelectrodes, display an excellent low-dimensional charge carrier transport, and promote surface electrocatalysis. The present work aims at the preparation and investigation of electrochemically modified SWCNT and graphene-based electrodes for applications in the field of biosensors. We initially studied SWCNT films and focused on their topography and surface composition, electrical and optical properties. Parallel to SWCNTs, graphene films were investigated. Higher resistance values were obtained in comparison with nanotubes films. The electrochemical surface modification of both electrodes was investigated following two routes (i) the electrografting of aryl diazonium salts, and (ii) the electrophylic addition of 1, 3-benzodithiolylium tetrafluoroborate (BDYT). Both the qualitative and quantitative characteristics of the modified electrode surfaces were studied such as the degree of functionalization and their surface composition. The combination of Raman, X-ray photoelectron spectroscopy, atomic force microscopy, electrochemistry and other techniques, has demonstrated that selected precursors could be covalently anchored to the nanotubes and graphene-based electrode surfaces through novel carbon-carbon formation.

Matrix Designs and Methods for Secure and Efficient Compressed Sensing

The idea of balancing the resources spent in the acquisition and encoding of natural signals strictly to their intrinsic information content has interested nearly a decade of research under the name of compressed sensing. In this doctoral dissertation we develop some extensions and improvements upon this technique's foundations, by modifying the random sensing matrices on which the signals of interest are projected to achieve different objectives. Firstly, we propose two methods for the adaptation of sensing matrix ensembles to the second-order moments of natural signals. These techniques leverage the maximisation of different proxies for the quantity of information acquired by compressed sensing, and are efficiently applied in the encoding of electrocardiographic tracks with minimum-complexity digital hardware. Secondly, we focus on the possibility of using compressed sensing as a method to provide a partial, yet cryptanalysis-resistant form of encryption; in this context, we show how a random matrix generation strategy with a controlled amount of perturbations can be used to distinguish between multiple user classes with different quality of access to the encrypted information content. Finally, we explore the application of compressed sensing in the design of a multispectral imager, by implementing an optical scheme that entails a coded aperture array and Fabry-Pérot spectral filters. The signal recoveries obtained by processing real-world measurements show promising results, that leave room for an improvement of the sensing matrix calibration problem in the devised imager.

Optical properties of a nanomatch-like plasmonic structure

The optical properties of a match-like plasmonic nanostructure are numerically investigated using full-wave finite-difference time-domain analysis in conjunction with dispersive material models. This work is mainly motivated by the developed technique enabling reproducible fabrication of nanomatch structures as well as the growing applications that utilize the localized field enhancement in plasmonic nanostructures. Our research revealed that due to the pronounced field enhancement and larger resonance tunabilities, some nanomatch topologies show potentials for various applications in the field of, e.g., sensing as well as a novel scheme for highly reproducible tips in scanning near field optical microscopy, among others. Despite the additional degrees of freedom that are offered by the composite nature of the proposed nanomatch topology, the paper also reflects on a fundamental complication intrinsic to the material interfaces especially in the nanoscale: stoichiometric mixing. We conclude that the specificity in material modeling will become a significant issue in future research on functionalized composite nanostructures.

PM(10) remote sensing from geostationary SEVIRI and polar-orbiting MODIS sensors over the complex terrain of the European Alpine region

The subject of this study is to investigate the capability of spaceborne remote sensing data to predict ground concentrations of PM10 over the European Alpine region using satellite derived Aerosol Optical Depth (AOD) from the geostationary Spinning Enhanced Visible and InfraRed Imager (SEVIRI) and the polar-orbiting MODerate resolution Imaging Spectroradiometer (MODIS). The spatial and temporal resolutions of these aerosol products (10 km and 2 measurements per day for MODIS, ∼ 25 km and observation intervals of 15 min for SEVIRI) permit an evaluation of PM estimation from space at different spatial and temporal scales. Different empirical linear relationships between coincident AOD and PM10 observations are evaluated at 13 ground-based PM measurement sites, with the assumption that aerosols are vertically homogeneously distributed below the planetary Boundary Layer Height (BLH). The BLH and Relative Humidity (RH) variability are assessed, as well as their impact on the parameterization. The BLH has a strong influence on the correlation of daily and hourly time series, whilst RH effects are less clear and smaller in magnitude. Despite its lower spatial resolution and AOD accuracy, SEVIRI shows higher correlations than MODIS (rSEV∼ 0.7, rMOD∼ 0.6) with regard to daily averaged PM10. Advantages from MODIS arise only at hourly time scales in mountainous locations but lower correlations were found for both sensors at this time scale (r∼ 0.45). Moreover, the fraction of days in 2008 with at least one satellite observation was 27% for SEVIRI and 17% for MODIS. These results suggest that the frequency of observations plays an important role in PM monitoring, while higher spatial resolution does not generally improve the PM estimation. Ground-based Sun Photometer (SP) measurements are used to validate the satellite-based AOD in the study region and to discuss the impact of aerosols' micro-physical properties in the empirical models. A lower error limit of 30 to 60% in the PM10 assessment from space is estimated in the study area as a result of AOD uncertainties, variability of aerosols properties and the heterogeneity of ground measurement sites. It is concluded that SEVIRI has a similar capacity to map PM as sensors on board polar-orbiting platforms, with the advantage of a higher number of observations. However, the accuracy represents a serious limitation to the applicability of satellites for ground PM mapping, especially in mountainous areas.

Effect of Pulse Depletion in a Brillouin Optical Time-Domain Analysis System

Energy transfer between the interacting waves in a distributed Brillouin sensor can result in a distorted measurement of the local Brillouin gain spectrum, leading to systematic errors. It is demonstrated that this depletion effect can be precisely modelled. This has been validated by experimental tests in an excellent quantitative agreement. Strict guidelines can be enunciated from the model to make the impact of depletion negligible, for any type and any length of fiber. (C) 2013 Optical Society of America

Determining the optical properties of a gelatin-TiO2 phantom at 780 nm

Tissue phantoms play a central role in validating biomedical imaging techniques. Here we employ a series of methods that aim to fully determine the optical properties, i.e., the refractive index n, absorption coefficient μa, transport mean free path ℓ∗, and scattering coefficient μs of a TiO2 in gelatin phantom intended for use in optoacoustic imaging. For the determination of the key parameters μa and ℓ∗, we employ a variant of time of flight measurements, where fiber optodes are immersed into the phantom to minimize the influence of boundaries. The robustness of the method was verified with Monte Carlo simulations, where the experimentally obtained values served as input parameters for the simulations. The excellent agreement between simulations and experiments confirmed the reliability of the results. The parameters determined at 780 nm are n=1.359(±0.002), μ′s=1/ℓ∗=0.22(±0.02) mm-1, μa= 0.0053(+0.0006-0.0003) mm-1, and μs=2.86(±0.04) mm-1. The asymmetry parameter g obtained from the parameters ℓ∗ and μ′s is 0.93, which indicates that the scattering entities are not bare TiO2 particles but large sparse clusters. The interaction between the scattering particles and the gelatin matrix should be taken into account when developing such phantoms.

Microwave remote sensing of stratospheric trace gases using digital Fast Fourier Transform spectrometers

The Institute of Applied Physics observes middle atmospheric trace gases, such as ozone and water vapour, by microwave radiometry. We report on the comparison of measurements using a novel digital Fast Fourier Transform and accousto optical spectrometers. First tests made on ground are presented as well as first experience about the use of such spectrometers under aircraft conditions.