Suchergebnisse

Waste generation, in general, increases with technological development, consequently the interest in environmental protection and health risks have grown in recent years. Therefore, it is necessary to develop strategies that has a beneficial impact on waste reuse and management trying to achieve sustainable development in which the resources used and the waste generated are minimised, as well as trying to achieve a circular economy, incorporating waste and co-products to new materials. This approach has already been included in the European Union waste strategies, prioritizing the prevention in waste generation, as well as the recycling and valorisation of wastes as alternative to their landfilling disposal. The main objective of this Doctoral Thesis was born out of the need to develop new efficient applications with commercial interest as construction materials (ceramics, cement and bricks), depending on the percentage of three types of inorganic residues: (1) Ilmenite mud generated in the production of TiO2 pigment, (2) phosphogypsum from the H3PO4 industry, and (3) construction and demolition waste (CDW). A number of instrumental techniques were deployed to characterise both the wastes used and the new materials designed, such as, X-ray diffraction (XRD), X-ray fluorescence (XRF), inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma optical emission spectrometry (ICP-OES), thermo-gravimetric analysis and differential scanning calorimetry (TGA/DSC) and scanning electron microscopy (SEM). In addition, the technological properties, such as resistance, water absorption, etc., have been compared in relation to traditional commercial materials and evaluated according to the established technical standards. Since, some of the wastes are considered NORM (Naturally Occurring Radioactive Material), the materials obtained were evaluated by alpha and gamma spectrometry, and the environmental implications (leaching and radiological studies) were evaluated. The most prominent findings of the present research can be divided under three main headings: Ilmenite mud Once the physical, chemical, granulometric, micro-structural and radiological properties of this waste were known, the design of new sulphur polymer cements and ceramic bodies adding different percentages were carried out. The results shown that ilmenite mud could be successfully immobilised and valorised as an additive. Theirs technological properties are in agreement with the requirements established in each regulations and, in some cases, the results were even better than those obtained by the reference materials. Finally, it can be concluded that that both materials can be used with negligible environmental impact or health risk. Phosphogypsum This waste has been valorised as an additive in ceramic manufacturing, complying with the international regulations for both technological properties and environmental requirements. Moreover, the addition up to 5 wt.% of phosphogypsum improves the technological properties in relation to the reference material. In addition, this waste has been studied as a calcium source for CO2 mineral sequestration and calcite production with high efficiencies (96 %). The study of the fluxes of metals and radionuclides showed that most of the phosphogypsum pollutants are transferred to calcite (> 95%). Construction and demolition waste (CDW) This waste has been recycled as substitute of natural aggregates to produce bricks. The results shown that low cost bricks with excellent technological properties can be obtained using CDW as an aggregate and lime or cement, as binders. ; La generación de residuos, en general, aumenta según incrementa el grado de desarrollo tecnológico de una sociedad, por lo que el interés por la protección del medio ambiente y los riesgos para la salud han florecido en los últimos años. Por tanto, desarrollar estrategias que mejoren la gestión de los residuos tratando de alcanzar un desarrollo sostenible en el que se minimicen los recursos utilizados y los residuos generados es muy necesario, así como tratar de alcanzar una economía circular, incorporando los residuos y co-productos a nuevos materiales. Este enfoque ya ha sido incluido en las estrategias de la Unión Europea en materia de residuos, priorizando la prevención en la generación de residuos, así como el reciclaje y la valorización de estos como alternativa a su depósito en vertedero. El objetivo principal de la presente Tesis Doctoral nace de la necesidad de desarrollar nuevas aplicaciones eficientes y de interés comercial en materiales de construcción (cerámicas, cementos y ladrillos), en base a diferentes porcentajes de tres tipos de residuos inorgánicos: (1) lodo de ilmenita generado en la producción de pigmento de TiO2, (2) fosfoyeso procedente de la industria del H3PO4, y (3) residuos de construcción y demolición (RCD). Para el estudio, tanto de la caracterización de los residuos como de los nuevos materiales diseñados, se han empleado diferentes técnicas instrumentales; entre otras, la difracción y la fluorescencia de rayos X (DRX/FRX), espectrometrías de masas o de emisión óptica con fuente de emisión por plasma de acoplamiento inductivo (ICP-MS/OES), análisis termo-gravimétrico y calorimétrico de barrido diferencial (TGA/DSC), y la microscopía electrónica de barrido (MEB). Las propiedades tecnológicas, como la resistencia, la absorción de agua, etc., han sido comparadas en relación a materiales comerciales tradicionales y evaluadas de acuerdo a los estándares técnicos establecidos. Como algunos de los residuos son considerados NORM (Naturally Occurring Radioactive Material = materiales radioactivos de origen natural), los materiales obtenidos fueron evaluados mediante espectrometría alfa y gamma, y también se evaluaron las implicaciones ambientales de su utilización (estudios de lixiviación y radiológicos). Los resultados más relevantes obtenidos de la presente Tesis Doctoral se pueden dividir en tres bloques: Lodo de ilmenita Una vez conocidas las propiedades físicas, químicas, granulométricas, micro-estructurales y radiológicas de este residuo se llevó a cabo el diseño de nuevos cementos poliméricos sulfurosos y cuerpos cerámicos, incorporando diferentes porcentajes. Los datos obtenidos demostraron que el lodo de ilmenita puede inmovilizarse y valorizarse con éxito al incluirlo como aditivo. Sus propiedades tecnológicas cumplieron sobradamente con los requisitos marcados en las diferentes regulaciones y, en algunos casos, fueron incluso mejores a las de los materiales de referencia. Finalmente, indicar que ambos materiales pueden ser usados sin generar problemas ambientales o de salud para las personas. Fosfoyeso Este residuo ha sido incluido como aditivo en cerámicas, las cuales has cumplido con las normativas internacionales vigentes en relación a las propiedades tecnológicas y con los requisitos ambientales establecidos. Incluso la adición de hasta 5 % de fosfoyeso mejora las propiedades tecnológicas en comparación al material de referencia. Este residuo también ha sido estudiado como fuente de calcio para el secuestro mineral del CO2 y obtención de calcita, obteniéndose altas eficiencias (96 %). El estudio de los flujos de metales y radionucleidos demostraron que la mayor parte de los contaminantes del fosfoyeso se transfieren a la calcita (> 95 %). RCD Este residuo ha sido reciclado como sustituto del agregado natural para la producción ladrillos. Los resultados muestran que pueden obtenerse ladrillos de bajo costo con excelentes propiedades físicas usando RCD como agregado, y cal o cemento como aglutinantes.

1. Introduction to Rheology -- 1.1 What is Rheology? -- 1.2 Why Rheological Properties are Important -- 1.3 Stress as a Measure of Force -- 1.4 Strain as a Measure of Deformation -- 1.4.1 Strain Measures for Simple Extension -- 1.4.2 Shear Strain -- 1.5 Rheological Phenomena -- 1.5.1 Elasticity; Hooke's Law -- 1.5.2 Viscosity -- 1.5.3 Viscoelasticity -- 1.5.4 Structural Time Dependency -- 1.5.5 Plasticity and Yield Stress -- 1.6 Why Polymeric Liquids are Non-Newtonian -- 1.6.1 Polymer Solutions -- 1.6.2 Molten Plastics -- 1.7 A Word About Tensors -- 1.7.1 Vectors -- 1.7.2 What is a Tensor? -- 1.8 The Stress Tensor -- 1.9 A Strain Tensor for Infinitesimal Deformations -- 1.10 The Newtonian Fluid -- 1.11 The Basic Equations of Fluid Mechanics -- 1.11.1 The Continuity Equation -- 1.11.2 Cauchy's Equation -- 1.11.3 The Navier-Stokes Equation 40 References -- 2. Linear Viscoelasticity -- 2.1 Introduction -- 2.2 The Relaxation Modulus -- 2.3 The Boltzmann Superposition Principle -- 2.4 Relaxation Modulus of Molten Polymers -- 2.5 Empirical Equations for the Relaxation Modulus -- 2.5.1 The Generalized Maxwell Model -- 2.5.2 Power Laws and an Exponential Function -- 2.6 The Relaxation Spectrum -- 2.7 Creep and Creep Recovery; The Compliance -- 2.8 Small Amplitude Oscillatory Shear -- 2.8.1 The Complex Modulus and the Complex Viscosity -- 2.8.2 Complex Modulus of Typical Molten Polymers -- 2.8.3 Quantitative Relationships between G*(?) and MWD -- 2.8.4 The Storage and Loss Compliances -- 2.9 Determination of Maxwell Model Parameters -- 2.10 Start-Up and Cessation of Steady Simple Shear and Extension -- 2.11 Molecular Theories: Prediction of Linear Behavior -- 2.11.1 The Modified Rouse Model for Unentangled Melts -- 2.11.1.1 The Rouse Model for Dilute Solutions -- 2.11.1.2 The Bueche Modification of the Rouse Theory -- 2.11.1.3 The Bueche-Ferry Law -- 2.11.2 Molecular Theories for Entangled Melts -- 2.11.2.1 Evidence for the Existence of Entanglements -- 2.11.2.2 The Nature of Entanglement Coupling -- 2.11.2.3 Reptation -- 2.11.2.4 The Doi-Edwards Theory -- 2.11.2.5 The Curtiss-Bird Model -- 2.11.2.6 Limitations of Reptation Models -- 2.12 Time-Temperature Superposition -- 2.13 Linear Behavior of Several Polymers 94 References -- 3. Introduction to Nonlinear Viscoelasticity -- 3.1 Introduction -- 3.2 Nonlinear Phenomena -- 3.3 Theories of Nonlinear Behavior -- 3.4 Finite Measures of Strain -- 3.4.1 The Cauchy Tensor and the Finger Tensor -- 3.4.2 Strain Tensors -- 3.4.3 Reference Configurations -- 3.4.4 Scalar Invariants of the Finger Tensor -- 3.5 The Rubberlike Liquid -- 3.5.1 A Theory of Finite Linear Viscoelasticity -- 3.5.2 Lodge's Network Theory and the Convected Maxwell Model -- 3.5.3 Behavior of the Rubberlike Liquid in Simple Shear Flows -- 3.5.3.1 Rubberlike Liquid in Step Shear Strain -- 3.5.3.2 Rubberlike Liquid in Steady Simple Shear -- 3.5.3.3 Rubberlike Liquid in Oscillatory Shear -- 3.5.3.4 Constrained Recoil of Rubberlike Liquid -- 3.5.3.5 The Stress Ratio (N1/?) and the Recoverable Shear -- 3.5.4 The Rubberlike Liquid in Simple Extension -- 3.5.5 Comments on the Rubberlike Liquid Model -- 3.6 The BKZ Equation -- 3.7 Wagner's Equation and the Damping Function -- 3.7.1 Strain Dependent Memory Function -- 3.7.2 Determination of the Damping Function -- 3.7.3 Separable Stress Relaxation Behavior -- 3.7.4 Damping Function Equations for Polymeric Liquids -- 3.7.4.1 Damping Function for Shear Flows -- 3.7.4.2 Damping Function for Simple Extension -- 3.7.4.3 Universal Damping Functions -- 3.7.5 Interpretation of the Damping Function in Terms of Entanglements -- 3.7.5.1 The Irreversibility Assumption -- 3.7.6 Comments on the Use of the Damping Function -- 3.8 Molecular Models for Nonlinear Viscoelasticity -- 3.8.1 The Doi-Edwards Constitutive Equation -- 3.9 Strong Flows; The Tendency to Stretch and Align Molecules -- References -- 4. Steady Simple Shear Flow and the Viscometric Functions -- 4.1 Introduction -- 4.2 Steady Simple Shear Flow -- 4.3 Viscometric Flow -- 4.4 Wall Slip and Edge Effects -- 4.5 The Viscosity of Molten Polymers -- 4.5.1 Dependence of Viscosity on Shear Rate -- 4.5.2 Dependence of Viscosity on Temperature -- 4.6 The First Normal Stress Difference -- 4.7 Empirical Relationships Involving Viscometric Functions -- 4.7.1 The Cox-Merz Rules -- 4.7.2 The Gleissle Mirror Relations -- 4.7.3 Other Relationships 176 References -- 5. Transient Shear Flows Used to Study Nonlinear Viscoelasticity -- 5.1 Introduction -- 5.2 Step Shear Strain -- 5.2.1 Finite Rise Time -- 5.2.2 The Nonlinear Shear Stress Relaxation Modulus -- 5.2.3 Time-Temperature Superposition -- 5.2.4 Strain-Dependent Spectrum and Maxwell Parameters -- 5.2.5 Normal Stress Differences for Single-Step Shear Strain -- 5.2.6 Multistep Strain Tests -- 5.3 Flows Involving Steady Simple Shear -- 5.3.1 Start-Up Flow -- 5.3.2 Cessation of Steady Simple Shear -- 5.3.3 Interrupted Shear -- 5.3.4 Reduction in Shear Rate -- 5.4 Nonlinear Creep -- 5.4.1 Time-Temperature Superposition of Creep Data -- 5.5 Recoil and Recoverable Shear -- 5.5.1 Creep Recovery -- 5.5.1.1 Time-Temperature Superposition; Creep Recovery -- 5.5.2 Recoil During Start-Up Flow -- 5.5.3 Recoverable Shear Following Steady Simple Shear -- 5.6 Superposed Deformations -- 5.6.1 Superposed Steady and Oscillatory Shear -- 5.6.2 Step Strain with Superposed Deformations -- 5.7 Large Amplitude Oscillatory Shear -- 5.8 Exponential Shear; A Strong Flow -- 5.9 Usefulness of Transient Shear Tests -- References -- 6. Extensional Flow Properties and Their Measurement -- 6.1 Introduction -- 6.2 Extensional Flows -- 6.3 Simple Extension -- 6.3.1 Material Functions for Simple Extension -- 6.3.2 Experimental Methods -- 6.3.3 Experimental Observations for LDPE -- 6.3.4 Experimental Observations for Linear Polymers -- 6.4 Biaxial Extension -- 6.5 Planar Extension -- 6.6 Other Extensional Flows -- References -- 7. Rotational and Sliding Surface Rheometers -- 7.1 Introduction -- 7.2 Sources of Error for Drag Flow Rheometers -- 7.2.1 Instrument Compliance -- 7.2.2 Viscous Heating -- 7.2.3 End and Edge Effects -- 7.2.4 Shear Wave Propagation -- 7.3 Cone-Plate Flow Rheometers -- 7.3.1 Basic Equations for Cone-Plate Rheometers -- 7.3.2 Sources of Error for Cone-Plate Rheometers -- 7.3.3 Measurement of the First Normal Stress Difference -- 7.4 Parallel Disk Rheometers -- 7.5 Eccentric Rotating Disks -- 7.6 Concentric Cylinder Rheometers -- 7.7 Controlled Stress Rotational Rheometers -- 7.8 Torque Rheometers -- 7.9 Sliding Plate Rheometers -- 7.9.1 Basic Equations for Sliding Plate Rheometers -- 7.9.2 End and Edge Effects for Sliding Plate Rheometers -- 7.9.3 Sliding Plate Melt Rheometers -- 7.9.4 The Shear Stress Transducer -- 7.10 Sliding Cylinder Rheometers -- References -- 8. Flow in Capillaries, Slits and Dies -- 8.1 Introduction -- 8.2 Flow in a Round Tube -- 8.2.1 Shear Stress Distribution -- 8.2.2 Shear Rate for a Newtonian Fluid -- 8.2.3 Shear Rate for a Power Law Fluid -- 8.2.4 The Rabinowitch Correction -- 8.2.5 The Schummer Approximation -- 8.2.6 Wall Slip in Capillary Flow -- 8.3 Flow in a Slit -- 8.3.1 Basic Equations for Shear Stress and Shear Rate -- 8.3.2 Use of a Slit Rheometer to Determine N1 -- 8.3.2.1 Determination of N1 from the Hole Pressure -- 8.3.2.2 Determination of N1 from the Exit Pressure -- 8.4 Pressure Drop in Irregular Cross Sections -- 8.5 Entrance Effects -- 8.5.1 Experimental Observations -- 8.5.2 Entrance Pressure Drop—the Bagley End Correction -- 8.5.3 Rheological Significance of the Entrance Pressure Drop -- 8.6 Capillary Rheometers -- 8.7 Flow in Converging Channels -- 8.7.1 The Lubrication Approximation -- 8.7.2 Industrial Die Design -- 8.8 Extrudate Swell -- 8.9 Extrudate Distortion -- 8.9.1 Surface Melt Fracture—Sharkskin -- 8.9.2 Oscillatory Flow in Linear Polymers -- 8.9.3 Gross Melt Fracture -- 8.9.4 Role of Slip in Melt Fracture -- 8.9.5 Gross Melt Fracture Without Oscillations -- References -- 9. Rheo-Optics and Molecular Orientation -- 9.1 Basic Concepts—Interaction of Light and Matter -- 9.1.1 Refractive Index and Polarization -- 9.1.2 Absorption and Scattering -- 9.1.3 Anisotropic Media; Birefringence and Dichroism -- 9.2 Measurement of Birefringence -- 9.3 Birefringence and Stress -- 9.3.1 Stress-Optical Relation -- 9.3.2 Application of Birefringence Measurements -- References -- 10. Effects of Molecular Structure -- 10.1 Introduction and Qualitative Overview of Molecular Theory -- 10.2 Molecular Weight Dependence of Zero Shear Viscosity -- 10.3 Compliance and First Normal Stress Difference -- 10.4 Shear Rate Dependence of Viscosity -- 10.5 Temperature and Pressure Dependence -- 10.5.1 Temperature Dependence of Viscosity -- 10.5.2 Pressure Dependence of Viscosity -- 10.6 Effects of Long Chain Branching -- References -- 11. Rheology of Multiphase Systems -- 11.1 Introduction -- 11.2 Effect of Rigid Fillers -- 11.2.1 Viscosity -- 11.2.2 Elasticity -- 11.3 Deformable Multiphase Systems (Blends, Block Polymers) -- 11.3.1 Deformation of Disperse Phases and Relation to Morphology -- 11.3.2 Rheology of Immiscible Polymer Blends -- 11.3.3 Phase-Separated Block and Graft Copolymers -- References -- 12. Chemorheology of Reacting Systems -- 12.1 Introduction -- 12.2 Nature of the Curing Reaction -- 12.3 Experimental Methods for Monitoring Curing Reactions -- 12.3.1 Dielectric Analysis -- 12.4 Viscosity of the Pre-gel Liquid -- 12.5 The Gel Point and Beyond -- References -- 13. Rheology of Thermotropic Liquid Crystal Polymers -- 13.1 Introduction -- 13.2 Rheology of Low Molecular Weight Liquid Crystals -- 13.3 Rheology of Aromatic Thermotropic Polyesters -- 13.4 Relation of Rheology to Processing of Liquid Crystal Polymers -- References -- 14. Role of Rheology In Extrusion -- 14.1 Introduction -- 14.1.1 Functions of Extruders -- 14.1.2 Types of Extruders -- 14.1.3 Screw Extruder Zones -- 14.2 Analysis of Single Screw Extruder Operation -- 14.2.

General Abstract 1. Introduction Nowadays, it is essential to develop and find new ways to reduce the increasing pollution deriving from anthropogenic and environmental sources. Human activities are major responsible of climate changes and ecosystems alterations, because of the increasing release of CO2 and other harmful gases inside the atmosphere. In order to reduce the environmental impact of the human society, a great attention is now given to such processes able to reduce the pollutants concentration in both air and water systems. Advanced oxidation processes (AOPs), which involves the generation of highly reactive hydroxyl radicals (OH•), have emerged as promising air and water treatment technology for the degradation or mineralization of a wide range of pollutants. Titanium dioxide (TiO2) induced photocatalysis is an example of AOP processes and it has been demonstrated its efficiency in the decomposition of various organic contaminants. TiO2 is a very well known and well-researched material due to the stability of its chemical structure, biocompatibility, physical, optical, and electrical properties. TiO2-based photocatalysts are used for a variety of applications such as degradation of volatile organic compounds (VOCs) [1] and decomposition of nitrogen pollutants (NOx) [2] or also organic dyes, like Methylene Blue [3]. The crystalline forms of TiO2 are anatase, rutile and brookite. In general, TiO2 is preferred in anatase form because of its high photocatalytic activity, non-toxicity, chemically stability; moreover, it is relatively inexpensive. For a long time, new synthetic routes have been developed to prepare nano-TiO2 samples in order to enhance their photocatalytic efficiency [4-6]. In fact, since many years the attention has been focused on ultrasmall semiconductive particles, because they show peculiar and enhanced properties compared to the micrometric particles ones [7]. Nano-sized TiO2 is extremely efficient towards the photodegradation processes; in particular, photo-redox reactions are greatly enhanced thanks to the high numbers of active sites present on the extremely large surface area [8]. However, in recent years many papers published the possible health risks correlated with nano-sized materials [9,10]. The small size, shape, solubility and agglomeration degree of nano-sized materials, make them able to cross the cell boundaries or pass directly from the lungs into the blood stream and finally reach all the organs in the body [11]. On the other hand, larger particles are adsorbed by organs and cells with more difficulty. The main question is then if it is necessary to use the nano-sized particles in an exclusive way. Kwon et al. [12] stated that nanocatalysts having small particle size, high surface area, and a high density of surface coordination unsaturated sites offer improved catalytic performance over microscale catalysts but this does not imply the impossibility a priori to use these latter in selected conditions. The use in photocatalysis of TiO2 powders with larger-sized crystallites is a very interesting approach to reduce the possible health problems caused by nanoparticles. 2. Aims of work The aims of this PhD work is to evaluate the photoactivity of micro-TiO2 samples using as irradiation source both UV and LED lights. At first, commercial powdered micro- and nano-sized TiO2 catalysts, were tested and then improved for the degradation of pollutants in both gas and aqueous phase. The ultimate purpose of the PhD work is to test the possibility of using TiO2 for production of building materials; the photocatalytic activity of TiO2 can be then exploited for degrading air pollutants inside domestic environments or workplaces, thus making them healthier over time. Application of photocatalysis to construction buildings began towards the end of 1980s with the production of photocatalytic glasses, which provided self-cleaning and anti-fogging properties [13]. Afterward photocatalytic cementitious materials have been patented by Mitsubishi Corp. and Italcementi SpA [14,15]. In all these construction materials, the active photocatalyst is anatase TiO2. Although the use of photocatalytic cement is still restricted and limited, many buildings and city roads have been designed and constructed since 2000. Relevant examples are Church "Dives in Misericordia", Rome, Italy; Music and Arts City Hall, Chamberéry, France [16]. In general, the mostly used powders of commercial TiO2 for photocatalytic applications are nanometric: this leads some advantages in terms of pollutants degradation efficiency, but many backwards too, like the difficulty to recover the catalyst or the possibility of inhalation with consequent health damage, even the high cost is not negligible. For this reasons, the optimization of the photocatalytic efficiency of micrometric compounds is desired, in order to replace definitely the nanometric catalysts. In this PhD work micro-sized TiO2 powder was used for the preparation of porcelain gres tiles, which are commercial manufactured products, opening a new generation of material intrinsically safer than the traditional photocatalytic products. All samples were fully characterized investigating textural, structural, morphological and surface properties. The photoefficiency was evaluated in different ways, which can be summarized as follows: • Assessment of the photoactivity of commercial samples, both nanometric and micrometric, in gas and aqueous phases in the presence of typical indoor and outdoor pollutants (NOx and Volatile Organic Compounds (VOCs), textile dyes, surfactants); • Assessment of the self-cleaning effect, evaluated by water contact angle measurements, during ultraviolet irradiation on micro-TiO2 tiles of building materials on whose surface the oleic acid is deposited (ISO/WD 27448-1); • Assessment of the effects of the addition of anionic or cationic ions, like fluorine, tin, rhenium or tungsten, on the catalytic surface through the impregnation method. Doping is useful to lower the titanium band gap and accordingly to increase the photocatalytic activity of the material. 3. Experimental details 3.1 Catalytic materials a) Preparation of TiO2 powders Different commercially available micro- and nano-sized pigmentary-powdered TiO2 were chosen; the catalysts were characterized and used without further treatment. In the Table 3.1 the photocatalytic powders used in this PhD work are reported. For each powder, the different physico-chemical characteristics are specified: XRD for the crystalline nature, BET for the surface area, XPS for the atomic composition of elements, SEM and TEM for the particles morphology, FTIR for the chemical composition of samples supported with DRS (diffuse reflectance spectra) for the characterization of the light absorption features and band-gap determinations. Before starting the photooxidation process of pollutants, commercial TiO2 powders were deposited in two plains of glass sample (each plain of 7.5x2.5 cm2). TiO2 powders (0.050 g) were first suspended in 2-propanol (50 ml) so to obtain a homogeneous suspension and then deposited by drop casting onto one side of the laminas. The solvent was simply evaporated at room temperature without any further treatment. The samples consisted in a thicker layer, obtained by overlapping three TiO2 coatings (labelled as T, standing for triple layers, followed by the substrate abbreviation), as shown in previous works by Bianchi et al. [17,18]. Table 3.1. Main features of TiO2-based commercial powders, used as photocatalysts, with the corresponding crystalline phase: nanometric and micrometric samples. Powder Crystalline phase BET (m2/g) Micro/Nano XPS OH/Otot P25 (Evonik) 75% anatase; 25% rutile 52 NANO 0.14 PC105 (Crystal) anatase 80 NANO 0.85 1077 (Kronos) anatase 11 MICRO 0.32 AH-R (Hundsman) anatase 12 MICRO 0.19 AT-1 (Crystal) anatase 12 MICRO 0.24 1001 (Kronos) anatase 11 MIXED PHASE (micro+nano) 0.27 1002 (Kronos) anatase 9 MIXED PHASE (micro+nano) 0.35 1071 (Kronos) anatase 10 MIXED PHASE (micro+nano) 0.18 A-Z (Hombitam) 99% anatase 4 MICRO 0.25 AN (Hombitam) 98,5% anatase 12 MICRO 0.5 N.10 (HombiKat) 98% anatase; 2% rutile 13 MICRO 0.13 b) Preparation of vitrified tiles Among all building materials, commercially available white tiles by GranitiFiandre SpA (sample name White Ground Active® (WGA) or Orosei Active) were chosen and used for the preparation of photocatalytic tiles. Porcelain gres tiles are manufactured under high pressure by dry-pressing of fine processed ceramic raw materials, with large proportions of quartz, feldspar, and other fluxes. The body of these materials is then fired at very high temperatures (1200–1300◦C) in kilns [19]. After impregnation with water, the tiles are subjected to temperature cycles between +5 and -5 °C, during a minimum of 100 freeze–thaw cycles, in order to verify their resistance to the frost and their durability. No evident cracks or damages were observed on the samples. The final material is thus characterized by lack of porosity, complete water-proofing, durability, hardness, wear resistance properties, and a complete frost resistance. The porcelain gres tiles were covered at the surface with a mixture of micro-TiO2 and a commercial SiO2-based compound prepared via ball–mill [20,21]. To achieve the desired product stability, at the end of the preparation procedure tiles were treated at high temperature (680 °C) for 80 min and then brushed to remove the powder present at the surface and not completely stuck. Temperature was precisely chosen to maintain the anatase form of the semiconductor and allow the vitrification of the tiles surface. Tiles were also prepared with the same procedure but without adding the photoactive oxide into the SiO2-based compound for the sake of comparison (sample name White Ground (WG) or Orosei)). The surface wettability of photoactive porcelain gres tiles was evaluated by static contact angle (CA) measurements performed with an OCA20 instrument (DataPhysics Co., Germany) equipped with a CCD camera and a 500 μL-Hamilton syringe to dispense liquid droplets. [22,23]. c) Doping effect on TiO2 powders Micrometric TiO2 powders were doped with cations like tungsten (W), tin (Sn) and rhenium (Re), and fluoride anions (F-). This was done with the aim to improve the photoefficiency of the micro-sized TiO2 catalysts, which have lower activity than the traditional nanopowders. Ren at al. [24] demonstrated that the fluorination of TiO2 nanocrystals gave a photocatalytic enhancement due to the higher separation efficiency of photogenerated electrons and holes. Furthermore, it has been found that the surface fluorination favors the generation of free OH radicals, which are responsible of an enhanced oxidation [25]. Regarding the doping with metal cations, in the literature is reported that Re dopant could effectively inhibit the recombination of the photoinduced electrons and holes [26]. Re can act as electron trap and promote the interfacial charge transfer processes in the composite systems, which reduces the recombination of photoinduced electron-hole pairs, thus improving the photocatalytic activity of TiO2. Moreover, it was demonstrated that that metal particles doping can facilitate the electron excitation by creating a local electrical field, enhancing photoinduced surface redox reactions: it results in the extension of the wavelength of TiO2 response towards the visible region [27]. The band gap energy of the doped-TiO2 results less than that of naked TiO2, which induces the red shift of the adsorption edge to respond to visible light. This peculiar feature gets interesting for the use of LED (Light Emission Diode) as irradiation source for the photooxidation processes, because LED emissions are located only in the visible region of light. In fact, an important aspect is the use of irradiation by visible light, through LED lamps. Several cities, like Milano, Stockholm, Los Angeles, Copenhagen, have chosen to adopt the LED emission for the outdoor illumination: Milano will substitute the 80% of urban illumination with the LED light within May 2015 (Expo start date). Advantages, connected to this emerging technology (high durability, cheapness, low energy consume), adhere very well with the environmental safety. Thus, NOx and VOCs photodegradation was performed with LED lamp, using micrometric doped powder. The classical impregnation method was applied to dope the catalyst surface with fluoride anions, starting from inorganic fluoride salts (NaF, NH4F, CaF2 and F2). At the end of the impregnation procedure (24 h, room temperature), powders were calcined at 400°C for 4 h and rinsed in distilled water three times. The metal doping was performed in two different ways: it was used the same procedure of impregnation method for tin (Sn) surface doping, whereas a different surface deposition technique (decoration method) was performed for metals of tungsten (W) and rhenium (Re). Decoration of M- or MO-NPs is commonly implemented by means of ultra-sounds (US) in aqueous or organic solutions where ceramics or polymer substrate powders are dispersed [28]. In the latter case, the precursor of metal was sonicated at a costant temperature of 80°C for 3 h, with 33.0% amplitude and a 50 W cm-2 intensity. At the end, the solution was centrifugated many times to remove all the solvent; the final powders was washed with n-pentane and centrifugated again. The residual solvent was evaporated and the sample was finally calcined at 480°C for 40 h to completely remove the organic scents. 3.2 Testing procedure a) Photocatalytic set-up in gas-phase Photocatalyitc degradation of air pollutants, such as acetone, acetaldehyde, toluene (well known as VOCs) and NOx, were conducted in Pyrex glass cylindrical reactors having different volume depending on the type of analyzed pollutant: 5 L for VOCs and 20 L for NOx, respectively. In the case of VOCs analysis, the gaseous mixture in the reactor was obtained by mixing hot chromatographic air (f.i. 250 ◦C for toluene), with relative humidity (RH) of 40%, and a fixed amount of volatilized pollutant, in order to avoid condensation. The initial concentration of VOCs in the reactor was 400 ppmv, monitored directly by micro-GC sampling. Photon sources were provided by a 500 W iron halogenide lamp (Jelosil, model HG 500) emitting in the 315–400 nm wavelength range (UV-A) at 30 Wm−2 or by a LED lamp, emitting into the visible region. Acetone and acetaldehyde degradation tests lasted for 2 h, whereas toluene tests for 6 h, due to the difficulty in degrading a molecule with an aromatic ring and with a complex degradation pathway [19]. For NOx photodegradation study, a first static experimental setup was obtained used the following conditions: RH: 50%, UV light of 10 Wm-2 (for TiO2 powders deposited on glass sheets) or 20 Wm-2 (for micro-sized TiO2 gres tiles), with a NOx starting value of 1000 ppb. The analytical procedure was reported by Bianchi et al. [21]. NOx degradation by TiO2 powders (always immobilized on a glass sheet) and photoactive tiles was conducted also in continuous conditions using a plug-flow reactor (with an effective volume of 0.025 L) built strictly following the ISO 22197-1 rule [29]. Experimental conditions were maintained as follows: RH: 40%, 20Wm−2, [NOx]inlet=500 ppb, and 180, 32.4, 9, and 4.2 L h−1 total flow, respectively. A chemiluminescent analyzer (Teledyne Instruments M200E) was used to check the conversion of the pollutant in both batch and plug-flow reactor setups. b) Photocatalytic set-up in aqueous-phase The photocatalytic apparatus was a 1 L glass stirred reactor equipped with an iron halogenide UV lamp (500 W, Jelosil® HG500) emitting light at wavelengths of 315–400 nm and able to irradiate the reactor with a specific power of 95 Wm-2, when TiO2 powder was used as catalyst. The UV lamp was placed beside the reactor, which was cooled with water at a temperature of 30 ± 0.5◦C, as reported previously by Gatto et al. [30]. TiO2 was introduced in the reactor at the beginning of each test (0.66 g/L for surfactant degradation and 0.1 g/L for textile dyes). The variation of the surfactant (PFOA) concentration in solution was monitored by total organic carbon (TOC) analysis and ionic chromatography. The PFOA initial concentration ([PFOA]0= 4 mM) was maintained lower than its critical micellar concentration (7.8 mM) in order to avoid the formation of emulsions during the kinetic tests. Samples (10 mL) of the reaction mixture were collected at different reaction times: typically at 0 min (before the start of the reaction), 30 min, 1 h, 2 h, 3 h, 4 h, 6 h and 9 h. Textile dyes, chosen for the photodegradation tests, were Rhodamine B (RhB), Methylene Blue (MB) and Crystal Violet (CV); dyes degradation was checked every 60 min by determining the dye concentration in the water solution by a UV–vis spectrophotometer analyzer (T60 UV–vis PG LTD instruments), using water as the reference. Pure CV has an absorbance maximum at 590 nm, RhB at 555 nm and MB around 670 nm. Textile dyes degradation was also performed using photoactive tiles, covered with the micrometric 1077 powder. For this aim, a cylindrical batch reactor of 1 L volume was used for dye degradation tests in presence of ten photoactive tiles (0.03 m2 total surface photoactive area) immersed into the liquid solution, as reported by Bianchi et al. [31]. Refrigeration was allowed by a cooling jacket. Two different lamps directly immersed into the dye solution were used with this setup: a typical germicidal 9 W UV-C lamp (Philips TUV BL-S, model AEPL-7913 mercury vapor low pressure), with a radiant power of 1 Wm-2 and a 125 W UV-A lamp (Jelosil, mercury vapor low pressure), with an illuminance of 65 Wm-2, in correspondence of the tiles surface. During photocatalytic tests, the TiO2 active faces of the tiles were turned towards the UV light. After each test, the tiles were simply washed using deionized water and acetone and then left in deionized water all night long. The same dyes solution (RhB, MB, CV) were used in the present setup at a concentration of 1 × 10−5 M. c) Self-cleaning effect The self-cleaning capability of TiO2 photoactive tiles was evaluated in two different ways: (1) through the measurement of the water contact angle (CA) (KRUSS GmbH) of a tile, after oleic acid deposition and UV irradiation (Jelosil, model HG 500) for 76 h and (2) through the monitoring, by a colorimeter, of the discoloration of dyes directly put on the tiles surfaces, after exposure to the sunlight (Milan – Italy, May 2012). For water CA measurements, a test piece of porcelain gres tile of 100 ± 2mm2 were pre-treated by ultraviolet irradiation of 20 Wm-2 for at least 24 hours. Then, the catalytic samples were dipped inside an oleic acid (Fluka, >80%) solution (0.5 vol%) in order to simulate a polluting condition. The presence of oleic acids on the tile surface modify its wettability. After UV irradiation it was measured the CA at an appropriate time interval, observing a continuous decrease of the CA values related to a degradation of the polluting agent. The measurement can be considered concluded when the contact angle value of the clean photocatalytic tile is restored, as before the oleic acid deposition. For comparison, the measurement is repeated on a sample similarly polluted with oleic acid, but left in the dark for 76 hours. Furthermore, it was taken a sample of porcelain gres tile, not containing TiO2, and it was immersed into oleic acid solution and irradiated, with the aim to evaluate the pure contribute of UV irradiation. Dyes degradation instead was monitored by Vis-spectrometer equipped with an integrated sphere (OceanOptics, USB400-VIS-NIR-ES). 1 μL of dyes, dissolved in water, was put on the tiles surface and left under the sunlight, whose power was continuously checked from 9 am to 5 pm every day by a radiometer DeltaOhm HD2012,2. A mean power irradiation value of 7.28 W/m2 was measured. The color analysis was performed using the CIEXYZ and CIELAB models [22]. 4. Results and discussion 4.1 Characterization results a) Powders characterization Anatase, evidenced by XRD patterns, is the unique polymorph present for all samples, except for P25 and N.10 (by Hombikat) powders, which exhibit even the rutile phase (25 and 2%, respectively). The crystallographic reflexes (1 0 1), (2 0 0) and (2 1 1) have been employed to calculate the average crystallites size of the various titania particles. P25 and PC105, commercial nanometric powders, have comparable crystallite size centered on 25 nm, while the other samples have values between 120 and 200 nm, confirming their micro-sized nature. These structural properties are reflected in their BET surface areas that are about 11-12 m2/g, which are much lower compared to the nano-sized ones (Table 3.1). For 1001, 1002, 1071 samples Sherrer calculation was not performed, as TEM analysis reveals the presence of both micro-sized and ultrafine fractions, as it is visible in Fig. 4.1, section d. HR-TEM and SEM images confirmed the average crystallites sizes extrapolated by XRD analysis; moreover, it was excluded the presence of ultrafine particles in 1007, AT-1, AH-R, A-Z, AN and N.10 powders. It can be evidenced that nano-sized materials perfectly fall within the "nano" definition: in fact, both samples are characterized by average particles size of 15-30 nm (Fig. 4.1, section a), closely packed features and roundish contours [19]. As for what concerns the other powders (1077, AT-1, AH-R, A-Z, AN, N.10), they all exhibit well crystallized particles possessing smooth edge and average diameter size in the 120-200 nm range (see Fig. 4.1, section b and c), with fringes patterns belonging to the TiO2 anatase polymorph. On the contrary, for 1001, 1002 and 1071 powders TEM images again confirm that they are composed by a mixture of both micro-sized crystallites and some ultrafine particles (Fig. 4.1, section d). The surface state of the TiO2 particles was analyzed by XPS. No significant differences can be appreciated in the Ti 2p region among all the present samples concerning the binding energies (BE) and the full width at half-maximum (FWHM) values. The peak of Ti 2p3/2 is always regular and the BE at about 458.5 ± 0.1 eV compares well with the data for Ti(IV) in TiO2 materials [32]. The analysis of the oxygen peaks exhibits the presence of more than one component, which can be attributed to lattice oxygen in TiO2 (529.9 eV) and to surface OH species (>531.5 eV) respectively. A particular O1s shape was observed for PC105. In this case, the OH component is very intense probably due to a particular industrial synthesis in order to enhance the photocatalytic efficiency of the sample. The hydrophilicity/hydrophobicity character of photocatalysts surface plays a crucial role in determining the adsorption step and thus the photocatalytic activity, at least in the degradation of pollutants [33]. P105 exhibits the highest concentration of OH that represent the 85% of the oxygen at the surface, as it shown in Fig. 4.2. It is noteworthy that the micro-sized samples, with the exception of N.10 (by HombiKat) sample, present a higher atomic concentration of OH groups in comparison with P25, pointing out the higher hydrophilic character of their surface (see Table 3.1, fifth column). Fig. 4.1. TEM images of the various TiO2 powders. Section a: P25; section b: 1077; section c: AH-R; section d: 1071. FTIR spectra in the ν(OH) spectral range of the samples in air revealed two complex absorption bands, respectively located in the 3000–3450 cm-1 range and at ν ≥ 3600 cm-1. Based on the spectral behavior and of our previous data [19], the former envelope can be ascribed to the stretching mode of all H-bonded OH groups present at the surface of the various solids, whereas the latter corresponds to the stretching mode of all Ti–OH species free from hydrogen bonding interactions [34]. It is well-known that surface hydroxyl radicals play a fundamental role in the photocatalytic processes [35]. In particular, photo-generated holes react with water molecules adsorbed on TiO2 surface, leading to the formation of OH•: TiO2 + hν → h+ + e- (3.1) h+ + H2O → OH• + H+ (3.2) The pigmentary TiO2 powders showed appreciable amounts of OH groups and this validate their rather good performances in the photocatalyitc degradation, as reported in our previous study [19]. Fig. 4.2. O1s XPS spectra for (a) P25; (b) PC105; (c) 1077; (d) AT-1. b) Gres tiles characterization XPS measurement reveals the presence of only Ti(IV) and a Ti/Si ratio of 0.15 for the micro-TiO2+SiO2-based compound, which belongs to porcelain grès tiles. The preservation of the pure anatase form was verified by both XRPD and XPS measurements. As reported by Anderson and Bard [37] the presence of SiO2, together with TiO2, enhances the formation of hydroxyl radical OH•, which may be achieved via strong Brønsted acid sites at the TiO2/SiO2 interface region. Such incorporation inhibits the crystal growth of TiO2 allowing the preservation of the anatase structure at high temperature. By the investigation of morphological features, the presence of SiO2-based compound is evident in gres tiles (Fig. 4.3), in the form of either small protruding particles or as amorphous coating which covers the TiO2 particles. Fig. 4.3. HR-TEM images of the TiO2 porcelain gres tiles materials. (a) refers to low magnification and (b) to high magnification. The very thin nature of these particles and/or coating allows to inspect the fringe patterns located below, confirming that the spacing among the fringes are still ascribable to the anatase TiO2 polymorph. 4.2 Photocatalytic tests 4.2.1 Photocatalytic activity in gas-phase a) NOx photoabatement with TiO2 powders In this section, several commercial pigmentary powders were tested for NOx degradation and were compared with the nanometric powders efficiency (P25 and PC105). At first, the tested concentration of NOx in the reactor was 1000 ppb, in order to follow the same pollutant concentration requested by the ISO 22197-1 rules [38]. All the samples showed good photocatalytic performances, because the abatement of NOx was early completed at the end of 3 hours, except the 1071 (by Kronos) sample, which showed lower photodegradation (61.5 %). The efficiency of the other samples was between 90 and 99%: this behavior leads to hypothesize a complete degradation of the pollutant within the chosen limited time of the run (3 h). In particular, it is interesting to observe the photodegradation trend of the only micro-sized samples (1077, AH-R, Hombitam A-Z, Hombitam AN and HombiKat N.10) at 15 min, 30 min, 60 min and 240 min, the most significantly times. In Fig. 4.4 we can observe the peculiar differences, which arise in the initial period of the degradation. 1077, Hombitam AZ and Hombitam AN seem to be the most active, showing the best efficiency in the first times of reaction (15, 30 min). This behavior can be explained through the physico-chemical features and the amount of hydroxyl radicals that initiate the oxidation of NO. The ratio of OH/Otot, obtained by XPS analysis, resulted to be, in fact, higher than the other micrometric ones (Table 3.1). In particular, after 2 h, the NOx conversion of these samples is higher than 90%, very close to that of P25, which reaches the complete pollutant degradation in the same time. Thus, even if the nano-sized materials (P25 and PC105) show the best performances, the photocatalytic activities of the pigmentary powders are comparable, in agreement with the presence of appreciable amount of surface hydroxyls, which are crucial species for the photooxidation processes [39]. From the trend in the Fig. 4.4 it is clear that the micrometric samples with the best photocatalytic performances are the ones showing the largest OH component, the following 1007, Hombitam AZ and Hombitam AN. Fig. 4.4. TiO2 commercial micro-sized powders (1077, AH-R, Hombitam AZ, Hombitam AN, HombiKat N.10) for NOx abatement at 15, 30, 60, 240 min under UV light irradiation. b) NOx photoabatement with photoactive tiles Another study concerns the application in photocatalysis of building materials. In this PhD work porcelain gres tiles, covered with micrometric TiO2 powder, were used for the NOx degradation, under UV light, in static experimental conditions in gas phase. Starting from 1000 ppb of NO2, i.e. the same amount required by the ISO 22197-1 specification, the 65% of degradation was measured after 6 h. A very interesting trend (Fig. 4.5) was observed also following the NO2 degradation by photocatalytic tiles. NO2 was chosen as specific reference pollutant instead of the more generic NOx, because of its higher hazardousness. The continued exposure to high NO2 levels, in fact, can contribute to the development of acute or chronic bronchitis [40]. More in detail, tests were carried out by using as starting pollutant concentration 106 ppb (value not to be exceeded more than 18 times in a calendar year), and 212 ppb (alert threshold), according to the Directive 2008/50/EC of the European Parliament, which states the guidelines for the protection of the human health. It is possible to observe (Fig. 4.5) that, as the amount of starting pollutant is decreased, the time necessary to bring its concentration under the limit required by the European Directive (21 ppb) also decreases. In the Fig. 4.5 inset the degradation trend can be observed in the case of an initial pollutant concentration close to the alert threshold. Fig. 4.5. Time necessary to degrade the pollutant and decrease its amount under the limit value required by the Directive 2008/50/EC of the European Parliament and of the council on ambient air quality and cleaner air for Europe (21 ppb); 20 W/m2, RH 50%, static conditions. Therefore under real pollution conditions, simulating a day in the absence of wind (static conditions) WGA is able to degrade NO2 in a very efficient way bringing the pollutant concentration down to the required limit (21 ppb) in a matter of hours [21]. Micro-sized TiO2 porcelain gres tiles were also tested in continuous conditions using a plug-flow reactor, whose the operating conditions have been softened cutting the inlet concentration by half (500 ppb, instead of 1000 ppb). It was investigated the role of the flow per hour on the final NO2 conversion. An interesting aspect revealed: the modification of the flow per hour leads to an evident change of the contact times that is the time the pollutant can stay "in contact" with the catalyst surface. As expected, increasing the contact time, the final conversion proportionally increases. This result is very evident for Orosei Active sample that shows a conversion varying from 1.3% to 82.0% at 180 L h−1 and 4.2 L h−1, respectively. The obtained 82% conversion at 4.2 L h−1 flow can be consequently considered a very good value. c) VOCs photoabatement with TiO2 powders In order to study the photocatalytic activity of nano- and micro-sized samples, the degradation of three different VOCs, acetone, acetaldehyde and toluene, has been performed. As an illustrative example, it was reported the toluene photodegradation tests. For both nano-and micro-sized TiO2 powders, the pollutant was not completely degraded, even after 6 h of reaction. Moreover, it is noteworthy that the degradation percentages fell more or less in the same range (46–52%) with a slightly higher value for the nanometric P25 and PC105 catalysts, as it is shown in Fig. 4.6. Toluene degradation resulted very difficult due to the complexity of molecule, which presents the aromatic ring. The different catalysts show similar behavior toward the toluene degradation, irrespective of their physico-chemical characteristics. On the contrary, the pollutant mineralization is rather different for almost all samples. Furthermore, a low amount of CO2 formation confirmed the incompleteness of the degradation reaction. The possible by-products, which could take form during the degradation, were monitored by FTIR measurements. After the employment in toluene degradation, the spectra of the materials underwent deep changes. In particular, it was possible to recognize signals of unreacted toluene (T) and of several by-products deriving from its degradation, among which benzyl alcohol (BZOH), benzoic acid (BZAc) and benzaldehyde (BZH) [19]. In addition, the signals due to the stretching mode (νOH) of Ti-OH species free from hydrogen bonding interactions were disappeared with the parallel increase of the broad envelope generated by H-bonded OH groups [31]. Thus, it was possible to state that the catalysts surface underwent irreversible changes after the employment in the photodegradation reaction of toluene: the photo-active "free" Ti-OH sites were completely absent, as a result of their participation to the reaction. Fig. 4.6. Toluene degradation histogram: photoefficiency achieved with commercial micro-sized TiO2 and compared to the P25 and PC105 ones (nanometric). Their disappearance was a clear evidence of why toluene degradation appeared incomplete even after 6 h of reaction for all the samples, regardless of the morphological features of the materials. Therefore, in the case of toluene and in general for all less hydrophilic VOCs, it was well evident that both micro-sized materials and nano-sized ones possess almost the same photocatalytic behavior. 4.2.2 Photocatalytic activity in aqueous-phase Parallel with photocatalytic tests in gas-phase, photodegradation of surfactants and textile dyes in aqueous phase were performed. In particular, the PFOA (perfluooroctanoic acid) was chosen as surfactant species. The abatement was conducted by using P25 nano-powder as catalyst. The photodegradation trend, monitored at different times, highlighted the incomplete PFOA mineralization. For the entire duration of the photo-abatement process, it was possible to observe a decrease in the PFOA content in solution. However, the mineralization after 4 h settled down: the fluoride content and the percentage mineralization after 6 and 9 h remained equal to 29% and 32%, respectively, as reported by Gatto et al. [29]. Through HPLC-MS analysis was confirmed the presence of the intermediates in the solution that took form through two possible degradation pathways: this surface modification might influence the catalyst reducing the photocatalytic efficiency of TiO2. Nevertheless, it is important to note that, as reported in the literature, no PFOA abatement was observed working in the presence of TiO2 as photocatalyst without UV irradiation as well as under UV irradiation in the absence of photocatalyst (photolysis) [31]. The other interesting study concerns the textile dyes photodegradation, using micro-sized TiO2 (1077) powders as catalysts. The textile dyes analyzed were Methylene Blue (MhB), Rhodamine B (RhB) and Crystal Violet (CV). Experimental dark tests showed a very low adsorption of all the dyes on both kinds of powders. The contribute of photolysis was almost negligible for MhB and CV, whereas 12% of dye degradation for simple photolysis (10% for P25) was achieved for RhB. Nano-sized powder showed the best results for all the considered dyes achieving the complete decolorizing of the water solution, but also micro-sized sample was able to degrade the pollutants with a good efficiency (ranging from 48 to 58% depending on the dye in six hours) (see Fig. 4.7), as reported by Bianchi et al. [30]. In addition, the micro-sized powder can be easily filtered and recovered in order to be immediately reused for further photodegradation reactions. In fact, 1077 was recovered by the simple centrifugation and reused in the same dye degradation test with no loss of photoactivity [30]. Fig. 4.7. Photocatalysis of dyes performed with powdered micro-TiO2 catalyst (1077): crystal violet □; methylene blue ▲; rhodamine B ◌. Another application is relative to the photocatalytic efficiency of TiO2 porcelain gres tiles, evaluated through UV-vis measurements. This choice reflects the fact that photoactive porcelain gres tiles are covered with the micrometric 1077 powder. It was observed an increase of about 15% of dyes degradation in comparison to the simply photolysis. These porcelain gres tiles can be reused, just after insertion of the tiles in distilled water, and without affecting the photocatalytic activity. In fact, all the tests were done using the same batch of ten samples of industrial tiles, and no loss in their photoactivity was monitored. This indicates that the TiO2 deposited layers are not deactivated during the reaction either by loss or poisoning of the catalyst, and can be reutilized in subsequent runs. Thus, these new industrial ceramic materials are surely an interesting alternative to TiO2 suspensions in photocatalytic applications avoiding the removal of the particles at the end of the process. 4.2.3 Self-cleaning effect A different aspect for the evaluation of gres tiles photo-efficiency is the CA evaluation, measured on micro-sized TiO2 porcelain gres tiles, after the deposition of oleic acid and irradiation by UV lamp. At first, before the oleic acid (Fluka, >80%) deposition, the pretreatment CA measurements were performed obtaining value of about 31°. The, the catalytic samples were dipped inside the oleic acid solution (0.5 vol%); the presence of oleic acids on the tile surface modify its wettability, the water contact angle in fact increases to about 65°. After UV irradiation it was measured the CA at an appropriate time interval, observing a continuous decrease of the CA values related to a degradation of the polluting agent. We observed that after 76 h of irradiation, the water CA reached the starting value before the oleic acid deposition (about 30°). This highlights the self-cleaning properties of TiO2 porcelain gres tile [22] and its photocatalytic efficiency for the degradation of organic contaminant deposited on the surface. On the contrary, the same kind of porcelain gres tile (Orosei Active), treated with oleic acid, but maintained in the dark, does not show modifications of CA in the range t0 and t76. The same procedure, consisting in the deposition of oleic acid solution and irradiation under UV light for 76 h, was performed for a porcelain gres tiles, not containing TiO2. Even in this case the CA measurement during the UV irradiation remained the same, i.e., the initial CA measured on the oleic acid film (65°). It is justified that the change in the value of the contact angle is due merely to the photodegradation of the oleic acid due to both the action of UV radiation and the photocatalytic efficiency of the used material and not by spontaneous degradation of oleic acid, induced by non photocatalytic factors. Thus, the photocatalytic process is necessary for the abatement of organic pollutants [17]. 4.3 Doping effect on TiO2 powders Micro-sized 1077 powder was even doped by the impregnation method. First of all the fluorination effect was investigated, making a comparison with the corresponding nanometric P25 powder: in both powders, after the fluorination, the photocatalytic activity of NOx and VOCs abatement resulted increased. The simply surface fluorination seems to be a good method to increase the photoactivity in commercial TiO2 samples, even with large crystallites [41]. In particular, the morphological features evidenced in the HR-TEM images and FT-IR spectral patterns, showed significant features. When the fluorination was carried out on the 1077 sample, there was an increasing of the OH groups interacting by H-bonding in F2 fluorination and new families of free OH groups involving Ca2+ and Na+ ions. The simple surface fluorination by fluorination resulted as an easy and good method to increase the photoactivity in commercial TiO2 samples, even with large crystallites, as reported in Fig. 4.8. Fig. 4.8. Toluene degradation for both micro- (1077) and nano-sized (P25) TiO2 samples, naked and fluorinated (NaF precursor). Physico-chemical characterization demonstrated that the surface fluorination influenced all the surface OH groups, leaving free only some particular OH "families", reasonably the more active in the photocatalytic process. Thus, the driving force of the process is both the presence of active OH population and the efficient adsorption of the pollutant molecules on the photocatalytic semiconductor surface. Parallel with this, the metal surface deposition with Sn, W and Re lead to an improved photoefficiency. In this case, micro-sized TiO2 powders exhibited a higher photoactivity compared with the naked TiO2 one. In particular, an interesting aspect was even the evaluation of photo-efficiency of doped 1077 using the LED light as irradiation source for the pollutant degradation. It has been observed that the photo-abatement efficiency of micro-sized catalysts for VOCs is improved by the presence of metals particles, in particular in the case of rhenium and tungsten. The degradation percentage of acetone was in fact, 37% for 1077_W and 33% for 1077_Re, compared with the 1077, which showed a negligible photoactivity (~2%), when the catalysts were irradiated by visible light. In Fig. 4.9 it is possible to see the improved photo-efficiency. In fact, the metal species like W and Re have the main properties of promote the charge transfer and the visible light absorption, which lead to enhanced photocatalytic degradation of pollutants than naked micro-sized TiO2, even under visible light irradiation [42]. Fig. 4.9. Acetone photodegradation in gas-phase under visible light (performed with a LED lamp). 5. Conclusions The photocatalytic activity of both nanometric and micrometric TiO2 powders was evaluated, revealing that nano-sized powders have the best photo-efficiency. However, commercial pigmentary micro-sized TiO2 powders have given good results proving that they could be good materials in photocatalysis and good alternative to nano-sized catalysts. In particular, 1077, Hombitam AZ and AN are the micro-sized TiO2 powders with the highest photoactivity for NOx abatement. The low surface area is not a discriminant factor if other features compensate it; the ratio of OH/O has a specific influence for the pollutants photodegradation together with the morphological features of particles. In fact, nanometric P25 is characterized by a significant higher amount of hydroxyl radicals, in agreement with the optimal efficiency in pollutants photodegradation. However, also pigmentary 1077, Hombitam AZ and AN samples show appreciable amount of OH• groups and this justifies their good catalytic performance. Furthermore, porcelain gres tiles, prepared entrapping micro-TiO2 at the SiO2 surface confirmed a stable and reproducible photocatalytic activity toward organic contaminants, such as dyes and NOx, in both liquid and gas phase. This indicates that these new industrial ceramic materials with micrometric TiO2 are surely an interesting application, which avoids the use of traditional nanomaterials in powder form for their preparation. In addition, the doping of micrometric TiO2 powders with anionic or cationic species highlighted the possibility to increase the catalytic performance obtaining comparable results with naked nanometric samples. And, as a consequence of the high demand of the use of LED lamps in the indoor and outdoor areas, the metal particles on the micrometric TiO2 surface confirmed their ability to adsorb visible light and to be considered sensitizers. To summarize, powders with large particles and low surface area can have good photoefficiency for the depollution abatement.

The analysis of articles and normative documents for quality control and regional origin of wines was carried out. Chemical composition of the grapes and the wine has been considered, qualitative and quantitative changes during vinification, maturation and aging of wine were shown. The basic group of compounds contents and ratios which determine the qualitative characteristics of wines, as well as have an important role in the formation of aroma and taste of the drink was found. The prerequisites for the development of the market of counterfeit products and wine falsification methods were discussed. The analysis of scientific literature and regulatory framework governing the quality of the wines on the territory of Russia and the European Union and the existing approaches to determine their authenticity was conducted, the advantages and disadvantages are shown. The examples of using different criteria for the establishment of natural and adulterated wines have been discussed, as well as their approaches to identify and create a comprehensive system of wine production quality evaluation using methods of physicochemical analysis. The main methodological approaches to establish a wine regional origin, combining the capabilities of modern methods of analysis, mathematical modeling and statistics are analyzed, examples of their use in practice are shown.Keywords: wine, methods of analysis, quality, authenticity, regional origin, falsification, mathematical modeling (Russian)DOI: http://dx.doi.org/10.15826/analitika.2014.18.4.001 Yu.F. Yakuba1, A.A. Kaunova2, Z.A. Temerdashev2, V.O. Titarenko2, A.A. Halafjan2 1North Caucasian Regional Research Institute of Horticulture and Viticulture of the Russian Academy of Agricultural Sciences, Krasnodar, Russian Federation2 Kuban State University, Krasnodar, Russian FederationREFERENCES1. Oganesiants L.A., Panasiuk A.L. [Statistical data on world production of wine]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2007, no. 2, pp. 6-7 (in Russian).2. Egorov E.A., Guguchkina T.I., Adzhiev A.M., Oseledtseva I.V. Geograficheskie zony proizvodstva vin i natsional'nykh kon'iakov (brendi) vysokogo kachestva na iuge Rossii [Geographical areas and national wine production of cognac (brandy) High quality in southern Russia]. Krasnodar: GNU SKZNIISiV; Prosveshchenie-Iug, 2013. 155 p. (in Russian).3. Ageeva N.M., Guguchkina T.I. Identifikatsiia i еkspertiza vinogradnykh vin i kon'iakov [Identification and examination of wines and brandies]. Krasnodar: GNU SKZNIISiV; Prosveshchenie-Iug, 2008. 174 p. (in Russian).4. Kosiura V.T., Donchenko L.V., Nadykta V.D. Osnovy vinodeliia [Basics of wine]. Moscow, DeLi print, 2004. 440 p. (in Russian).5. Demin D.P., Zinchenko V.I., Zagoruiko V.A., Kosiura V.T. [Ways to improve the stability of port wines]. Trudy In-ta Magarach [Proceedings. Magaraci Institute], 1991, pp. 55-58 (in Russian).6. Nilov V.I., Skurikhin I.M. Khimiia vinodeliia i kon'iachnogo proizvodstva [Chemistry of winemaking and cognac production]. Moscow, Pishchepromizdat. 1960. 272 p. (in Russian).7. Sobolev E.M. Tekhnologiia natural'nykh i spetsial'nykh vin [Technology of natural and special wines]. Maikop: GURIPP «Adygeia», 2006. 400 p. (in Russian).8. Nuzhnyi V.P. [Modern ideas about the toxic properties of wine and food]. Vinograd i vino Rossii [Grapes and wine Russia], 1996, no. 2, pp. 29-32 (in Russian).9. Savchuk S.A. [Quality control and identification authentication cognacs chromatographic methods]. Metody otsenki sootvetstviia [Methods for assessing compliance], 2006, no. 8, pp. 18-25 (in Russian).10. Kozub G.I., Mamakova Z.A., Skorbanova E.A., Maksimova A.S. [Changing components of the chemical composition of sherry at his endurance]. Sadovodstvo, vinogradarstvo i vinodelie Moldavii [Horticulture, viticulture and winemaking Moldova], 1982, no. 1, pp. 33-36 (in Russian).11. Kishkovskii Z.N., Skurikhin I.M. Khimiia vina [Wine chemistry]. Moscow, Agropromizdat, 1988. P. 45-67 (in Russian).12. Filippovich Iu.B. Osnovy biokhimii [Fundamentals of Biochemistry]. Moscow, Agar, 1999. 507 p. (in Russian).13. Iakuba Iu. F. Analitika i tekhnologiia vinogradnykh distilliatov [Research and Technology grape distillates]. Moscow, Moscow University Publ., 2013. 168 p. (in Russian).14. Joon-Young J., Yun H. S., Lee J., Oh M.-K. Production of 1,2-Propanediol from Glycerol in Saccharomyces cerevisiae. J. Microbiol. Biotechnol., 2011, vol. 21, no. 8, pp. 846-853. doi:10.4014/jmb.1103.03009.15. Karpov S.S., Valuiko G.G., Nalimova A.A., Keptine A.I. [Some features of the formation of esters during fermentation of grape must]. Sadovodstvo, vinogradarstvo i vinodelie Moldavii [Horticulture, viticulture and winemaking Moldova], 1982, no. 2, pp. 31-33 (in Russian).16. Rodopulo A.K. Osnovy biokhimii vinodeliia [Fundamentals of Biochemistry winemaking]. Moscow, Legkaia i pishchеvaia promyshlеnnost' Publ., 1983. 240 p. (in Russian).17. Stabnikov V.N. Peregonka i rektifikatsiia еtilovogo spirta [Distillation and Rectification of ethyl alcohol]. Moscow, Pishchеvaia Promyshlennost' Publ., 1969. 456 p. (in Russian).18. Marinchenko V.A., Smirnov V.A. Tekhnologiia spirta [Technology of alcohol]. Moscow, Legkaia i pishchеvaia promyshlеnnost' Publ., 1981. 416 p. (in Russian).19. Strukova V.E. Karbonilamidnye reaktsii i ikh intensifikatsiia pri teplovoi obrabotke kreplenykh vin. Avtoref. diss. kand. [Reaction of carbonilamid and their intensification during the thermal treatment of fortified wines. Cand. sci. diss. abstract.]. Krasnodar, 1983. 26 p. (in Russian).20. Shol'ts E.P., Ponomarev S.V. Tekhnologiia pererabotki vinograda [Technology conversion of grapes]. Moscow, Agropromizdat, 1990. 447 p. (in Russian).21. Negrul' A.M., Gordeeva L.N., Kalmykova T.I. Ampelografiia s osnovami vinogradarstva. Uchebnoе posobiе dlia tekhnolog. vuzov [Ampelography the basics of viticulture. Textbook for technological universities]. Moscow, Vysshaia shkola Publ., 1979. 199 p. (in Russian).22. Pazo M., Almitfro E., Traveao C. Perfil de ammoacidos libres de los vinos Albarino у Godello. Alimfiitami, 2004, vol. 41, no 357, pp. 111-117.23. Khristiuk V.T., Uzun L.M., Baryshev M.G. [Ferment grape juice and pulp after treatment with extremely low frequency electromagnetic field range]. Izvеstiia vuzov. Pishchevaia tekhnologiia [Proceedings of the universities. Food technology], 2002, no. 5-6, pp.43-44 (in Russian).24. Herbert P., Barros P., Alves A. Detection of port wine imitation by discriminant analysis using free amino acids profiles. Amer. J. Enol. And Viticult., 2000, vol. 51, no.3, pp. 262-268.25. Ough C.S., Stashak R.M. Further studies on proline concentration in grapes and wines. Am. J. Enol. Vitic., 1974, vol. 25, no. 1, pp. 7-12.26. Iakuba Iu.F. [Direct determination of the basic amino acids of wine]. Zavodskaia laboratoriia. Diagnostika materialov [Industrial Laboratory. Diagnostics of materials], 2010, vol. 76, no. 4, pp.12-14 (in Russian).27. Iakuba Iu.F. [Direct determination of phenylalanine, tryptophan and tyrosine residues in wines]. Zavodskaia laboratoriia. Diagnostika materialov [Industrial Laboratory. Diagnostics of materials], 2008, vol. 74, no. 2, pp. 15-18 (in Russian).28. Bakker J., Bridle P., Timberlake C.F. The colours, pigment and phenol contents of young port wines: Effects of cultivar, season and site. Vitis, 1986, vol. 25, pp. 40-52.29. Etievant P., Schlich P., Bertrand A. Varietal and geographic classification of French red wines in terms of pigments and flavonoid compounds. J. Sci. Food Agric., 1988, vol. 42, pp. 39-54.30. Jackson M.G., Timberlake C.F., Bridle P. Red wine quality: Correlations between colour, aroma and flavor and pigment and other parameters of young Beaujolais. J. Sci. Food Agric., 1978, vol. 29, pp. 715-727.31. Joslyn M. A., Little A. Relation of type and concentration of phenolics to the color and stability of rose wines. Am. J. Enol. Vitic., 1967, vol. 18, pp. 138-148.32. Ramos R.A, Andrade P.В., Seabra R., Pereira C., Ferreira M.A., Faia M.A. Preliminary study of noncoloured phenolics in wines of varietal white grapes (codega, gouveio and malvasia fina): effects of grape variety, grape maduration and technology of winemaking. Food Chem., 1999, vol. 67, pp. 39-44.33. Valuiko G.G. Biokhimicheskie osnovy tekhnologii krasnykh vin. Avtoref. diss.dokt. tekhn. nauk [Biochemical basis of technology red wines. Dr. techn. sci. diss. abstract]. Krasnodar, 1972. 74 p. (in Russian).34. McDonald M.S., Hughes M.M., Burns J., Lean M.E.J., Matthews D., Crozier A. Survey of the free and conjugated myricetin and quercetin content of red wines of different geographical origins. J. Agric. Food Chem., 1998, vol. 46, pp. 368-375.35. Delgado R., Pedro M. Evolucion de la composicion fenolica de las uvas tintas durante la maduracion. Alimenlaria, 2001, vol. 38, no. 326, pp. 139-145.36. Christie P.J., Alfenito M.R., Walbot V. Impact of low-temperature stress on general phenylpropanoid and anthocyanin pathways: Enhancement of transcript abundance and anthocyanin pigmentation in maize seedlings. Planta, 1994, vol. 194, pp. 541-549.37. Macheix J.J., Sapis J.C., Fleuriet A. Phenolic compounds and polyphenoloxidase in relation to browning in grapes and wines. Crit. Rev. Food Sci. Nutr., 1991, vol. 30, pp. 441-486.38. Graham T.L. Flavonoid and isoflavonoid distribution in developing soybean seedling tissue and in seed and root exudates. Plant Physiol., 1991, vol. 95, pp. 594-603.39. Kliewer W.M. Influence of temperature, solar radiation and nitrogen on coloration and composition of emperor grapes. Am. J. Enol. Vitic., 1977, vol. 28, pp. 96-103.40. Tiutiunik V.I. Dinamika antotsianov pri sozrevanii i khranenii iagod nekotorykh standartnykh i gibridnykh sortov vinograda v predgornoi zone Kryma. Avtoref. diss. kand. biol. nauk [Anthocyan dynamics in berries ripening and storage of some standard and hybrid grape varieties in the foothill zone of Crimea. Kand. biol. sci. diss. abstract]. Kishinev, 1969. 21 p. (in Russian).41. Yinrong Lu., Yeap Foo L. Unexpected rearrangement of pyranoanthocyanidins to furoanthocyanidins. Tetrahedron Letters, 2002, vol. 43, pp. 715-718.42. Dallas C., Laureano O. Effect of SO2 on the extraction of individual anthocyanins and colored matter of three Portuguese grape varieties during winemaking. Vitis, 1994, vol. 33, pp. 41-47.43. Revilla I., Gonzalez-Sanjose M. Compositional changes during the storage of red wines treated with pectolytic enzymes: low molecular-weight phenols and flavan-3-ol derivative levels. Food Chemistry, 2003, vol. 80, pp. 205-214.44. Piermattei B., Amatti A., Castellari M. Preliminary studies on the use of dried grape stems in red winemaking. Vitis: Viticult., 2000, vol. 39, no. 1-2, pp. 4-46.45. Oganesiants L.A. Dub i vinodelie [Oak and winemaking]. Moscow, Agropishchepromizdat, 2001. 359 p. (in Russian).46. del Alamo Sanza M., Dominguez I. Nevares, Corcel L.M. Analysis for low molecular weight phenolic compounds in a red wine aged in oak chips. Anal. Chim. Acta, 2004, vol. 513, pp. 229-237.47. Atanasova V., Fulcrand H., Cheynier V. Effect of oxygenation on polyphenol changes occurring in the course of wine-making. Anal. Chim. Acta, 2002, vol. 458, pp. 15-27.48. Mateus N., Freitas V. De Evolution and stability of anthycyanin-derived pigments during port wine aging. J. Agr. and Food Chem., 2001, vol. 49, no. 11, pp. 5217-5222.49. Magomedov Z.B., Makuev G.A. [Coloring and phenolics substances varieties of grapes and the dynamics of their content in wines with aging]. Khranenie i pererabotka sel'khozsyr'ia [Storage and processing of agricultural], 2001, no. 10, pp. 51-50 (in Russian).50. GOST R 55242-2012. Vina zashchishchennykh geograficheskikh ukazanii i vina zashchishchennykh naimenovanii mesta proiskhozhdeniia. Obshchie tekhnicheskie usloviia [State Standard 55242-2012. Wines from protected geographical indications and wines with a protected place of origin. General specifications]. Moscow, Standartinform Publ., 2013. 12 p. (in Russian).51. GOST R 52523–2006. Vina stolovye i vinomaterialy stolovye. Obshchie tekhnicheskie usloviia [State Standard 52523–2006. Table wines and wine materials. General specifications]. Moscow, Standartinform Publ., 2008. 12 p. (in Russian).52. GOST R 52195–2003. Vina aromatizirovannye. Obshchie tekhnicheskie usloviia [State Standard 52195–2003. Flavored wine. General specifications]. Moscow, Standartinform Publ., 2009. 8 p. (in Russian).53. GOST R 52404–2005. Vina spetsial'nye i vinomaterialy spetsial'nye. Obshchie tekhnicheskie usloviia [State Standard 52404–2005. Wines and special wine materials. General specifications]. Moscow, Standartinform Publ., 2006. 8 p. (in Russian).54. GOST R 51158–2009. Vina igristye. Obshchie tekhnicheskie usloviia [State Standard 51158–2009. Sparkling wines. General specifications]. Moscow, Standartinform Publ., 2009. 8 p. (in Russian).55. SanPiN 2.3.2.1078–01. Gigienicheskie trebovaniia bezopasnosti i pishchevoi tsennosti pishchevykh produktov [Sanitary Standard 2.3.2.1078–01. Hygienic safety and nutritional value of foods]. 144 p. (in Russian).56. Nikolaeva M.A., Polozhishnikova M.A. Identifikatsiia i obnaruzhenie fal'sifikatsii prodovol'stvennykh tovarov: uchebnoe posobie [Identification and determination of falsification of food products: a tutorial]. Moscow, «FORUM»: INFRA-M Publ., 2009. 464 p. (in Russian).57. Holmberg L. Wine fraud. International Journal of Wine Research, 2010, vol. 2, pp. 105-113. doi:10.2147/IJWR.S14102.58. Martin G.J. The chemistry of chaptalization. Endowour, New Series, 1990, vol. 14, no. 3. pp. 137-143. doi:10.1016/0160-9327(90)90007-E.59. Ogrinc N., Kosir I.J., Spangenberg J.E., Kidric J. The application of NMR and MS methods for detection of adulteration of wine, fruit juices, and olive oil. A review. Anal. Bioanal. Chem., 2003, vol. 376, pp. 424-430. doi:10.1007/s00216-003-1804-6.60. Savchuk S.A., Vlasov V.N. [Identification of wine products using high performance liquid chromatography and spectrometry]. Vinograd i vino Rossii [Grapes and wine Russia], 2000, no. 5, pp. 5-13 (in Russian).61. GOST R 51149–98. Produkty vinodel'cheskoi promyshlennosti. Upakovka, markirovka, transportirovanie i khranenie [State Standard 51149–98. Wine industry products. Packaging, labeling, transportation and storage]. Moscow, Standartinform Publ., 2009. 6 p. (in Russian).62. GOST R 51074-2003. Produkty pishchevye. Informatsiia dlia potrebitelia. Obshchie trebovaniia [State Standard 51074-2003. Foodstuffs. Information for Consumers. general requirements]. Moscow, Standartinform Publ., 2006. 23 p. (in Russian).63. GOST R 51653-2000. Alkogol'naia produktsiia i syr'e dlia ee proizvodstva. Metod opredeleniia ob«emnoi doli еtilovogo spirta [State Standard 51653-2000. Alcoholic products and raw materials for its production. Method of determining of the ethanol volume fraction]. Moscow, Standartinform Publ., 2009. 6 p. (in Russian).64. GOST 13192-73. Vina, vinomaterialy i kon'iaki. Metod opredeleniia sakharov [State Standard 13192-73. Wine, brandy and wine materials. Method of sugars determination]. Moscow, Standartinform Publ., 2011. 10 p. (in Russian).65. GOST R 51621-2000. Alkogol'naia produktsiia i syr'e dlia ee proizvodstva. Metody opredeleniia massovoi kontsentratsii titruemykh kislot [State Standard 51621-2000. Alcoholic products and raw materials for its production. Methods of determination of the mass concentration of titratable acid]. Moscow, Standartinform Publ., 2009. 5 p. (in Russian).66. GOST R 51654-2000. Alkogol'naia produktsiia i syr'e dlia ee proizvodstva. Metod opredeleniia massovoi kontsentratsii letuchikh kislot [State Standard 51654-2000. Alcoholic products and raw materials for its production. Method of determination of the mass concentration of volatile acids]. Moscow, Standartinform Publ., 2009. 7 p. (in Russian).67. GOST R 51620-2000. Alkogol'naia produktsiia i syr'e dlia ee proizvodstva. Metod opredeleniia massovoi kontsentratsii privedennogo еkstrakta [State Standard 51620-2000. Alcoholic products and raw materials for its production. Method of determination of the mass concentration of the powered extract]. Moscow, Standartinform Publ., 2009. 6 p. (in Russian).68. GOST R 52391-2005. Produktsiia vinodel'cheskaia. Metod opredeleniia massovoi kontsentratsii limonnoi kisloty [State Standard 52391-2005. Wine products. Method of determination of the mass concentration of citric acid]. Moscow, Standartinform Publ., 2007. 8 p. (in Russian).69. GOST R 51655-2000. Alkogol'naia produktsiia i syr'e dlia ee proizvodstva. Metod opredeleniia massovoi kontsentratsii svobodnogo i obshchego dioksida sery [State Standard 51655-2000. Alcoholic products and raw materials for its production. Method of determination of free and total sulfur dioxide]. Moscow, Standartinform Publ., 2009. 6 p. (in Russian).70. GOST R 51766-2001. Syr'e i produkty pishchevye. Atomno-absorbtsionnyi metod opredeleniia mysh'iaka [State Standard 51766-2001. Raw materials and food products. Determination of arsenic using Atomic absorption spectroscopy]. Moscow, Standartinform Publ., 2011. 10 p. (in Russian).71. GOST R 51823-2001. Alkogol'naia produktsiia i syr'e dlia ee proizvodstva. Metod inversionno-vol'tamperometricheskogo opredeleniia soderzhaniia kadmiia, svintsa, tsinka, medi, mysh'iaka, rtuti, zheleza i obshchego dioksida sery [State Standard 51823-2001. Alcoholic products and raw materials for its production. Determination of cadmium, lead, zinc, copper, arsenic, mercury, iron and total sulfur dioxide using voltamperometry]. Moscow, Standartinform Publ., 2009. 18 p. (in Russian).72. GOST 26927-86. Syr'e i produkty pishchevye. Metody opredeleniia rtuti [State Standard 26927-86. Raw materials and food products. Methods of determination of mercury]. Moscow, Standartinform Publ., 2010. 15 p. (in Russian).73. GOST 26930-86. Syr'e i produkty pishchevye. Metod opredeleniia mysh'iaka [State Standard 26930-86. Raw materials and food products. Method of the determination of arsenic]. Moscow, Standartinform Publ., 2010. 6 p. (in Russian).74. GOST 26932-86. Syr'e i produkty pishchevye. Metody opredeleniia svintsa [State Standard 26932-86. Raw materials and food products. Methods of determination of lead]. Moscow, Standartinform Publ., 2010. 11 p. (in Russian).75. GOST 26933-86. Syr'e i produkty pishchevye. Metody opredeleniia kadmiia [State Standard 26933-86. Raw materials and food products. Methods of determination of cadmium]. Moscow, Standartinform Publ., 2010. 10 p. (in Russian).76. GOST 30178-96. Syr'e i produkty pishchevye. Atomno-absorbtsionnyi metod opredeleniia toksichnykh еlementov [State Standard 30178-96. Raw materials and food products. Determination of toxic elements using atomic absorption spectroscopy]. Moscow, Standartinform Publ., 2010. 8 p. (in Russian).77. GOST 30538-97. Produkty pishchevye. Metodika opredeleniia toksichnykh еlementov atomno-еmissionnym metodom [State Standard 30538-97. Foodstuffs. Analysis of toxic elements using atomic-emission methods]. Moscow, Standartinform Publ., 2010. 27 p. (in Russian).78. Panasiuk A.L., Babaeva M.I. [Quality criteria for white wines of the New World]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2013, no. 5. pp. 22-24 (in Russian).79. Tochilina R.P. [About improvement of methods for the identification of wine production]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2007, no. 2. pp. 14-15 (in Russian).80. Tochilina R.P [Wine production quality and the problem of its identification]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2001, no. 3, pp. 8-9 (in Russian).81. GOST R 52813-2007. Produktsiia vinodel'cheskaia. Metody organolepticheskogo analiza [State Standard 52813-2007. Wine products. Sensory analysis methods]. Moscow, Standartinform Publ., 2008. 13 p. (in Russian).82. GOST R ISO 3972–2005. Organolepticheskii analiz. Metodologiia. Metod issledovaniia vkusovoi chuvstvitel'nosti [State Standard 3972–2005. Sensory analysis. Methodology. Methods of investigation of taste sensitivity]. Moscow, Standartinform Publ., 2006. 7 p. (in Russian).83. Kushnereva G.K., Guguchkina T.I., Pankin M.I., Lopatina L.I. [Investigation of table wines quality from physical and chemical parameters using mathematical]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2011, no. 4. pp. 18-21 (in Russian).84. Vina i alkogol'nye napitki. Direktivy i reglamenty Evropeiskogo Soiuza [Wines and alcoholic drinks. EU directives and regulations]. Moscow, IPK Standards Publ., 2000. 616 p. (in Russian).85. International Organisation of Vine and Wine http://www.oiv.int/ (accessed 02.07.14)86. Yakuba Yu. F., Guguchkina T.I., Ageeva N.M., Lopatina L.M. Sposob opredeleniia kachestva vinogradnogo vina [A method of determining of the wine quality]. Patent RF, no. 2310192, 2007. (in Russian).87. Kushnereva E.V., Guguchkina T.I. [Development of criteria for authenticity naturally semi-sweet and semi-dry wines]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2012, no. 5-6, pp. 70-72 (in Russian).88. Panasiuk A.L., Kuz'mina E.I., Zakharov M.A., Kharlamova L.N., Kornilina I.A. ["Ash and alkalinity" as indicators in the system of the authentication criteria of table wines]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2011, no. 1, pp. 20-21 (in Russian).89. Cliff M.A., King M.C., Schlosser J. Anthocyanin, phenolic composition, colour measurement and sensory analysis of BC commercial red wines. Food Research International, 2007, vol. 40, pp. 92–100. doi:10.1016/j.foodres.2006.08.002.90. González G., Peña-Méndez E.M. Multivariate data analysis in classification of must and wine from chemical measurements. Eur. Food Res. Technol., 2000, vol. 212, pp. 100–107. doi:10.1007/s002170000207.91. Lunina L.V., Guguchkina T.I., Ageeva N.M., Iakuba Iu.F. [The criteria of determining of the authenticity of wines]. Partnery i konkurenty [Partners and competitors], 2005, no. 5, pp. 27-29 (in Russian).92. Ageeva N.M., Guguchkina T.I., Markovskii M.G. [Once again about falsification of wines]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2002, no. 4, pp. 22-23 (in Russian).93. Valgina L.V., Zhirova V.V., Smirnova E.A. [Identification of wine production]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2010, no. 1, pp. 10-11 (in Russian).94. Sеn'kina Z.E., Arbuzov V.N., Aleshkin B.M. [Instrumental methods of analysis for the identification of grape wines]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2004, no. 1, pp. 25-27 (in Russian).95. Dergunov A.V., Lopin S.A., Il'iashenko O.I. [Influence of the biochemical composition of perspective white wine grapes on the quality of wine production]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2012, no. 4, pp. 22-25 (in Russian).96. Valgina L.A. Razrabotka kompleksnoi tovarovednoi otsenki i identifikatsii stolovykh polusladkikh vin. Dis. kand. tеkhn. nauk [Development of a comprehensive assessment and identification semi sweet wines Cand. tehn. sci. diss.]. Moscow, 2011. 147 p. (in Russian).97. Larionov A.B., Tokmin D.G., Sarvarova N.N., Marchenko I.A., Gerasimov M.K. [5-hydroxymethyl content as an additional indicator of the quality of alcoholic beverages]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2013, no. 5, pp. 25-27 (in Russian).98. Yakuba Yu. F., Guguchkina T.I., Ageeva N.M., Lopatina L.M., Lunina L.V. Sposob opredeleniia kachestva stolovogo vinogradnogo vina [Method of determining the quality of table grape wine]. Patent RF, no. 2312342, 2007 (in Russian).99. Sobolev Е.M., Kudlai D.V. Sposob opredeleniia natural'nosti belykh vin [Method of determining of the naturalness of white wines]. Patent RF, no. 2271000, 2006 (in Russian).100. Sarvarova N.N., Marchenko I.A., Rizvanov I.Kh., Tokmin D.G. [Determination of polyols by GC-MS without extraction for quality evaluation of the table wines]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2012, no. 6, pp. 16-20 (in Russian).101. Panasiuk A.L., Kuz'mina E.I., Kharlamova L.N., Zakharov M.A., Kadykova N.E., Babaeva M.V. [Controlled parameters of the natural wines. White wines of Chile]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2008, no. 4, pp. 8-11 (in Russian).102. Iakuba Iu.F., Lozhnikova M.S. [Improving of the analytical control of wine products]. Analitika i kontrol' [Analysis and control], 2011, vol. 15, no. 3, pp. 309-312 (in Russian).103. Kushnereva E.V., Markovskii M.G., Guguchkina T.I., Ageeva N.M. [Determination of biogenic amines in the vines]. Izvestiia vuzov. Pishchevaia tekhnologiia [Proceedings of the universities. Food technology], 2012, no. 1, pp. 106-108 (in Russian).104. Martuscelli M., Arfelli G., Manetta A.C., Suzzi G. Biogenic amines content as a measure of the quality of wines of Abruzzo (Italy). Food Chemistry., 2013, vol. 140, pp. 590–597. doi:10.1016/j.foodchem.2013.01.008.105. Leitгo M. C., Marques A. P., San Romгo M. V. A survey of biogenic amines in commercial Portuguese wines. Food Control., 2005, vol. 16, pp. 199-204. doi:10.1016/j.foodcont.2004.01.012.106. Soufleros E.H., Bouloumpasi E., Tsarchopoulos C., Biliaderis C.G. Primary amino acid profiles of Greek white wines and their use in classification according to variety, origin and vintage. Food Chem., 2003, vol. 80, no. 2, pp. 261-273. doi:10.1016/S0308-8146(02)00271-6.107. Zakharova A.M., Kartsova L.A., Grinshtein I.L. [Determination of organic acids, carbohydrates or sweeteners in food products and dietary supplements using HPLC]. Analitika i kontrol' [Analysis and control], 2013, vol. 17, no. 2, pp. 204-210 (in Russian).108. GOST R 52841-2007. Produktsiia vinodel'cheskaia. Opredelenie organicheskikh kislot metodom kapilliarnogo еlektroforeza [State Standard 52841-2007. Wine products. Determination of organic acids by capillary electrophoresis]. Moscow, Standartinform Publ., 2008. 7 p. (in Russian).109. Skorbanova E.A., Kairiak N.F., Mamakova Z.A. [Modern methods of detection of falsified wines]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2005, no. 6, pp. 26-27 (in Russian).110. Jackowetz J.N., Mira de Orduсa R. Survey of SO2 binding carbonyls in 237 red and white table wines. Food Control, 2013, vol. 32, pp. 687-692. doi:10.1016/j.foodcont.2013.02.001.111. Bodorev M.M., Subbotin B.S. [Chromatographic analysis of aromatic aldehydes and acids in wine]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2001, no. 1, pp. 19-21 (in Russian).112. Polozhishnikova M.A., Perelygin O.N. [Determination of the biological value and identification of red wines using content of flavanols phenolic acids]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2005, no. 6, pp. 22-24 (in Russian).113. Bridle P., Garcia-Viguera C. A simple technique for the detection of red wine adulteration with elderberry pigments. Food Chemistry, 1996, vol. 55, no. 2, pp. 111-113. doi:10.1016/0308-8146(95)00179-4.114. Tochilina R.P., Peschanaia V.A., Poznanskaia E.V., Goncharov S.A., Larina S.M. [About the problem of wines identifying. Effect on total pentose sugars in table wines]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2011, no. 1, pp. 13 (in Russian).115. GOST R 53193-2008. Napitki alkogol'nye i bezalkogol'nye. Opredelenie kofeina, askorbinovoi kisloty, konservantov i podslastitelei metodom kapilliarnogo еlektroforeza [State Standard 53193-2008. Alcoholic and non-alcoholic drinks. Determination of caffeine, ascorbic acid, preservatives, and sweeteners by capillary electrophoresis]. Moscow, Standartinform Publ., 2010. 11 p. (in Russian).116. Fauhl C, Wittkowski R, Lofthouse J, Hird S, Brereton P, Versini G, Lees M, Guillou C. Gas Chromatographic/Mass Spectrometric Determination of 3-Methoxy-1,2-Propanediol and Cyclic Diglycerols, By-Products of Technical Glycerol, in Wine: Interlaboratory Study. Journal of AOAC International, 2004, vol. 87, no. 5, pp. 1179-1188.117. Nieuwoudt H.H., Prior B.A., Pretorius S., Bauer F.F. Glycerol in South African Table Wines: An Assessment of its Relationship to Wine Quality. S. Afr. J. Enol. Vitic., 2002, vol. 23, no. 1, pp. 22-30.118. GOST R 53154-2008. Vina i vinomaterialy. Opredelenie sinteticheskikh krasitelei metodom kapilliarnogo еlektroforeza [State Standard 53154. Wine and wine materials. Determination of synthetic dyes by capillary electrophoresis]. Moscow, Standartinform Publ., 2010. 11 p. (in Russian).119. Zhirov V.M., Presniakova O.P., Neudakhina O.K., Doronin M.B. [Qualitative and quantitative analysis of elements in wines using ICP-MS]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2012, no. 6, pp. 30-31 (in Russian).120. Kolesnov A.Iu., Filatova I.A., Zadorozhniaia D.G., Maloshitskaia O.A. [Mass spectrometry of stable oxygen isotopes 18O/16O in wine production to establish its authenticity]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2012, no. 6, pp. 10-15 (in Russian).121. Zhirova V.V., e.a. Sposob opredeleniia proiskhozhdeniia organicheskikh oksikislot v vinakh i sokosoderzhashchikh napitkakh [Determination of the origin of organic hydroxy acids in wine and juice drinks]. Patent RF, no. 2487348, 2013. 12 с. (in Russian).122. Calderone G., Guillou C. Analysis of isotopic ratios for the detection of illegal watering of beverages. Food Chemistry, 2008, vol. 106, pp. 1399-1405. doi:10.1016/j.foodchem.2007.01.080.123. Guyon F., Gaillard L., Salagoïty M.-H., Médina B. Intrinsic ratios of glucose, fructose, glycerol and ethanol 13C/12C isotopic ratio determined by HPLC-co-IRMS: toward determining constants for wine authentication. Anal. Bioanal. Chem., 2011, vol. 401, pp. 1551-1558. doi:10.1007/s00216-011-5012-5.124. Cabaňero A.I., Recio J.L., Rupérez M. Isotope ratio mass spectrometry coupled to liquid and gas chromatography for wine ethanol characterization. Rapid Commun. Mass Spectrom., 2008, vol. 22. pp. 3111-3118. doi:10.1002/rcm.3711.125. Cabaňero A.I., Recio J.L., Rupérez M. Simultaneous stable carbon isotopic analysis of wine glycerol and ethanol by liquid chromatography coupled to isotope ratio mass spectrometry. J. Agric. Food Chem., 2010, vol. 58, pp. 722-728. doi:10.1021/jf9029095.126. Versinia G., Camina F., Ramponia M., Dellacassa E. Stable isotope analysis in grape products: 13C-based internal standardization methods to improve the detection of some types of adulterations. Analytica Chimica Acta, 2006, vol. 563, pp. 325-330. doi:10.1016/j.aca.2006.01.098.127. Kravchenko S.N., Kagan E.S., Stoletova A.A. [Development of mathematical model for assessing the quality of products]. Izvestiia vuzov. Pishchevaia tekhnologiia [Proceedings of the universities. Food technology], 2011, no. 4, pp. 105-109 (in Russian).128. Perelygin O.N. Ustanovlenie podlinnosti sukhikh vinogradnykh vin na osnove fiziko-khimicheskikh pokazatelei. Diss. kand. tekhn. nauk [Authentication of the dry wines using physical and chemical parameters. Cand. tehn. sci. diss.]. Moscow, 2004. 140 p. (in Russian).129. Charlton A. J., Wrobel M.S., Stanimirova I., Daszykowski M., Grundy H. H., Walczak B. Multivariate discrimination of wines with respect to their grape varieties and vintages. Eur. Food Res. Technol., 2010, vol. 231, pp. 733-743. doi:10.1007/s00217-010-1299-2.130. Košir I. J., Kocjancic,M., Ogrinc N., Kidrič J. Use of SNIF-NMR and IRMS in combination with chemometric methods for the determination of chaptalisation and geographical origin of wines (the example of Slovenian wines). Analytica Chimica Act, 2001, vol. 429, pp. 195-206. doi:10.1016/S0003-2670(00)01301-5.131. Gavrilina V.A. Metodologiia kontrolia vina raspoznavaniem. Diss. Dokt.tekhn. nauk [Methodology control wine using recognition. Dr. tehn. sci. diss.]. Orel, 2013. 259 p. (in Russian).132. Sidorova A.A., Ganzha O.V. Sposob identifikatsii ob«ekta putem postroeniia ego kharakteristicheskogo еlektroforeticheskogo profilia [Method of object identification by building its characteristic electrophoretic profile]. Patent RF, no. 2327978, 2008. 7 с. (in Russian).133. Ageeva N.M., Guguchkina T.I., Iakuba Iu.F. Sposob ustanovleniia natural'nosti vina [Method for establishing natural wine]. Patent RF, no. 2156976, 2000 (in Russian).134. Markosov V.A., Ageeva N.M., Guguchkina T.I., Iakuba Iu.F., Gaponov A.I. [Evaluation of the quality of special wines "Anapa strong" and "Cahors"]. Vinograd i vino Rossii [Grapes and wine Russia], 2001, no. 4, pp. 45-46 (in Russian).135. Gavrilina V.A., Mal'tseva O.I., Bulgakov D.S., Sychev S.N., Sychev K.S. [Application of principal component analysis to identify and compare natural wines. Part 2: Criteria of identity and similarity of dry red wines using a combination of principal component analysis and HPLC with spectrophotometric detection]. Vinodelie i vinogradarstvo [Wine-making and Viticulture], 2007, no. 3, pp. 30-32 (in Russian).136. Petrov V.I. Razrabotka skhemy identifikatsii natural'nykh vin po rezul'tatam ikh mul'tiеlementnogo analiza. Diss. kand. khim. nauk [Development of natural wines identification scheme based on the results of their multielement analysis. Cand. chem. sci. diss.]. Krasnodar, 2013. 157 p. (in Russian).137. Aramina A.A., Sadovoi V.V. [Assessment of compliance with regulatory requirements of wine production]. Izvestiia vuzov. Pishchevaia tekhnologiia [Proceedings of the universities. Food technology], 2011, no. 5-6, pp. 92-94 (in Russian).138. Duchowicz P.R., Giraudo M.A., Castro E.A., Pomilio A.B. Amino acid profiles and quantitative structure–property relationship models as markers for Merlot and Torrontes wines. Food Chemistry, 2013, vol. 140, pp. 210-216. doi:10.1016/j.foodchem.2013.02.064.139. Urbano M., Luque de Castro M. D., Pérez P. M., García-Olmo J., Gómez-Nieto M. A. Ultraviolet–visible spectroscopy and pattern recognition methods for differentiation and classification of wines. Food Chemistry. 2006, vol. 97, pp. 166-175. doi:10.1016/j.foodchem.2005.05.001.140. Guilln D., Palma M., Natera R., Romero R., Barroso C. G. Determination of the Age of Sherry Wines by Regression Techniques Using Routine Parameters and Phenolic and Volatile Compounds. J. Agric. Food Chem., 2005, vol. 53, pp. 2412-2417. doi:10.1021/jf048522b.141. Gerzhikova V.G., Zagoruiko V.A. [Quality control methods of the wine products]. Vinodelie i vinogradarstvo [Winemaking and Viticulture], 2003, no. 5, pp. 24-26 (in Russian).142. Arozarena I., Casp A., Marin R., Navarro M. Multivariate differentiation of Spanish red wines according to region and variety. Journal of the Science of Food and Agriculture. 2000, vol. 80, pp.1909-1917. doi:10.1002/1097-0010(200010)80:133.0.CO;2-U.143. Stupakova R.K., Sergeev E.N. [Wine quality control]. Vinodelie i vinogradarstvo [Winemaking and Viticulture], 2001, no. 4, pp. 15 (in Russian).144. Seeber R., Sferlazzo G., Leardi R., Dalla Serra A., Versini G. Multivariate data analysis in classification of musts and wines of the same variety according to vintage year. J. Agric. Food Chem., 1991, vol 39, no. 10, pp 1764-1769. doi:10.1021/jf00010a014.145. Perestrelo R., Barros A.S., Cámara J.S., Rocha S.M. In-Depth Search Focused on Furans, Lactones, Volatile Phenols, and Acetals As Potential Age Markers of Madeira Wines by Comprehensive Two-Dimensional Gas Chromatography with Time-of-Flight Mass Spectrometry Combined with Solid Phase Microextraction. J. Agric. Food Chem., 2011, vol. 59, pp. 3186-3204. doi:10.1021/jf104219t.146. Paneque P., Álvarez-Sotomayor Ma T., Clavijo A., Gómez I.A. Metal content in southern Spain wines and their classification according to origin and ageing. Microchemical Journal, 2010, vol. 94, pp. 175-179. doi:10.1016/j.microc.2009.10.017.147. Cuadros-Inostroza A., Giavalisco P., Hummel J., Eckardt A., Willmitzer L., Penfia-CorteÏs H. Discrimination of wine attributes by metabolome analysis. Analytical Chemistry, 2010, vol. 82, pp. 3573-3580. doi:10.1021/ac902678t.148. Khiabakhov T.S. [Basic conditions for the development of good practice winemaking]. Vinodelie i vinogradarstvo [Winemaking and Viticulture], 2011, no. 5, pp. 8-9 (in Russian).149. Galitskaia Iu.N., Martynova T.A. [Perspectives of development of the wine industry on Kuban]. Izvestiia vuzov. Pishchevaia tekhnologiia [Proceedings of the universities. Food technology], 2006, no. 4, pp. 9-12 (in Russian).150. Kaishev V.G., Usachev A.M. [Viticulture and winemaking Russia. Development of production for 1999-2003., problems and prospects]. Vinodelie i vinogradarstvo [Winemaking and Viticulture], 2004, no. 2, pp. 4-8 (in Russian).151. Tolokov N.R. [Legal regulation of wines by origin in Russia]. Vinodelie i vinogradarstvo [Winemaking and Viticulture], 2005, no. 2, pp. 9-10 (in Russian).152. Di Paola-Naranjo R.D, Baroni M.V, Podio N.S, Rubinstein H.R, Fabani M.P, Badini R.G, Inga M, Ostera H.A, Cagnoni M, Gallegos E, Gautier E, Peral-Garcia P, Hoogewerff J, Wunderlin D.A. Fingerprints for Main Varieties of Argentinean Wines: Terroir Differentiation by Inorganic, Organic, and Stable Isotopic Analyses Coupled to Chemometrics. J. Agric. Food Chem., 2011, vol. 59, pp. 7854-7865. doi:10.1021/jf2007419.153. Kallithraka S., Arvanitoyannis I.S., Kefalas P., El-Zajouli A., Soufleros E., Psarra E. Instrumental and sensory analysis of Greek wines; implementation of principal component analysis (PCA) for classification according to geographical origin. Food Chemistry, 2001, vol. 73, pp. 501-514. doi:10.1016/S0308-8146(00)00327-7.154. Nuñez M., Peсa R.M., Herrero C., Garcia-Martin S. Analysis of some metals in wine by means of capillary electrophoresis. Application to the differentiation of Ribeira Sacra Spanish red wines. Analusis, 2000, vol. 28, pp. 432-437. doi:10.1051/analusis:2000129.155. Galgano F., Favati F., Caruso M., Scarpa T., Palma A. Analysis of trace elements in southern Italian wines and their classification according to Provenance. LWT—Food Science and Technology, 2008, vol. 41, pp. 1808-1815. doi:10.1016/j.lwt.2008.01.015.156. Díaz C., Conde J.E., Estévez D., Pérez Olivero S.J., Pérez Trujillo J.P. Application of multivariate analysis and artificial neural networks for the differentiation of red wines from the Canary Islands according to the Island of origin. J. Agric. Food Chem., 2003, vol. 51, pp. 4303-4307. doi:10.1021/jf0343581.157. Soler F., Garcia-Rodrigues G., Perez-Lopez M., Hernandez-Moreno D. Characterization of "Ribera del Guadiana" and "Mйntrida" Spanish red wines by chemometric techniques based on their mineral contents. Journal of Food and Nutrition Research, 2011, vol. 50, no. 1, pp. 41-49.158. Frías S., Pérez Trujillo J., Peña E., Conde J. E. Classification and differentiation of bottled sweet wines of Canary Islands (Spain) by their metallic content. Eur. Food Res. Technol., 2001, vol. 213, pp. 145-149. doi:10.1007/s002170100344.159. Frías S., Conde J.E., RodrıÏguez-Bencomo J.J., GarcıÏa-Montelongo F., Pérez Trujillo J.P. Classification of commercial wines from the Canary Islands (Spain) by chemometric techniques using metallic contents. Talanta, 2003, vol. 59, pp. 335-344. doi:10.1016/S0039-9140(02)00524-6.160. Kruzlicova D., Fiket Ź., Kniewald G. Classification of Croatian wine varieties using multivariate analysis of data obtained by high resolution ICP-MS analysis. Food Research International, 2013, vol. 54, pp. 621-626. doi:10.1016/j.foodres.2013.07.053.161. Mar Castiñeira Gómez del M., Feldmann I., Jakubowski N., Andersson J.T. Classification of German white wines with certified brand of origin by multielement quantitation and pattern recognition techniques. J. Agric. Food Chem., 2004, vol. 5, pp. 2962-2974. doi:10.1021/jf035120f.162. Boschetti W., Rampazzo R.T., Dessuy M.B., Vale M.G., de Oliveira Rios A., Hertz P., Manfroi V., Celso P.G., Ferrгo M.F. Detection of the origin of Brazilian wines based on the determination of only four elements using high-resolution continuum source flame AAS. Talanta, 2013, vol. 111, pp. 147-155. doi:10.1016/j.talanta.2013.02.060.163. Moreno I.M, González-Weller D., Gutierrez V., Marino M., Cameán A.M., González A.G., Hardisson A. Differentiation of two Canary DO red wines according to their metal content from inductively coupled plasma optical emission spectrometry and graphite furnace atomic absorption spectrometry by using Probabilistic Neural Networks. Talanta, 2007, vol. 72, pp. 263-268. doi:10.1016/j.talanta.2006.10.029.164. Rodrigues S.M., Otero M., Alves A.A., Coimbra J., Coimbra M.A., Pereira E., Duarte A.C. Elemental analysis for categorization of wines and authentication of their certified brand of origin. Journal of Food Composition and Analysis, 2011, vol. 24, no. 4–5, pp. 548-562. doi:10.1016/j.jfca.2010.12.003.165. Bentlin F.R.S., Pulgati F.H., Dressler V.L., Pozebon D. Elemental analysis of wines from South America and their classification according to country. Journal of the Brazilian Chemical Society, 2011, vol. 22, no. 2, pp. 327-336. doi:10.1590/S0103-50532011000200019.166. Gonzalvez A., Llorens A., Cervera M.L., Armenta S., de la Guardia M. Elemental fingerprint of wines from the protected designation of origin Valencia. Food Chemistry, 2009, vol. 112, pp. 26-34. doi:10.1016/j.foodchem.2008.05.043.167. Geana I., Iordache A., Ionete R., Marinescu A., Ranca A., Culea M. Geographical origin identification of Romanian wines by ICP-MS elemental analysis. Food Chemistry, 2013, vol. 138, pp. 1125–1134. doi:10.1016/j.foodchem.2012.11.104.168. Coetzee P.P., Steffens F.E., Eiselen R.J., Augustyn O.P., Balcaen L., Vanhaecke F. Multi-element analysis of South African wines by ICP-MS and their classification according to geographical origin. J. Agric. Food Chem., 2005, vol. 53, pp. 5060-5066. doi:10.1021/jf048268n.169. Cozzolino D., Cynkar W.U., Shah N., Smith P.A. Can spectroscopy geographically classify Sauvignon Blanc wines from Australia and New Zealand?. Food Chemistry, 2011, vol. 126, pp. 673-678. doi:10.1016/j.foodchem.2010.11.005.170. Liu L., Cozzolino D., Cynkar W.U., Dambergs R.G., Janik L., O'Neill B.K., Colby C.B., Gishen M. Preliminary study on the application of visible–near infrared spectroscopy and chemometrics to classify Riesling wines from different countries. Food Chemistry, 2008, vol. 106, pp. 781-786. doi:10.1016/j.foodchem.2007.06.015.171. Heberger K., Csomos E., Simon-Sarkadi S.L. Principal component and linear discriminant analyses of free amino acids and biogenic amines in hungarian wines. J. Agric. Food Chem., 2003, vol. 51, pp. 8055-8060. doi:10.1021/jf034851c.172. Galgano F., Caruso M., Perretti G., Favati F. Authentication of Italian red wines on the basis of the polyphenols and biogenic amines. European Food Research and Technology, 2011, vol. 232, pp. 889-897. doi:10.1007/s00217-011-1457-1.173. Jaitz L., Siegl K., Eder R., Rak G., Abranko L., Koellensperger G., Hann S. LC-MS/MS analysis of phenols for classification of red wine according to geographic origin, grape variety and vintage. Food Chemistry, 2010, vol. 122, pp. 366-372. doi:10.1016/j.foodchem.2010.02.053.174. Arozarena I., Casp A., Marin R., Navarro M. Differentiation of some Spanish wines according to variety and region based on their anthocyanin composition. European Food Research and Technology, 2000, vol. 212, pp. 108-112. doi:10.1007/s002170000212.175. Rastija V., Srečnik G., Marica-Medić-Šarić. Polyphenolic composition of Croatian wines with different geographical origins. Food Chemistry. 2009, vol. 115, pp. 54-60. doi:10.1016/j.foodchem.2008.11.071.176. Li Z., Pan Q., Jin Z., Mu L., Duan C. Comparison on phenolic compounds in Vitisvinifera cv. Cabernet Sauvignon wines from five wine-growing regions in China. Food Chemistry, 2011, vol. 125, pp. 77-83. doi:10.1016/j.foodchem.2010.08.039.177. Bellomarino S.A., Conlan X.A., Parker R.M., Barnett N.W., Adams M.J. Geographical classification of some Australian wines by discriminant analysis using HPLC with UV and chemiluminescence detection. Talanta, 2009, vol. 80, pp. 833-838. doi:10.1016/j.talanta.2009.08.001.178. Rebolo S., Peсa R.M., Latorre M.J., GarcıÏa S., Botana A.M., Herrero C. Characterization of Galician (NW Spain) Ribeira Sacra wines using pattern recognition analysis. Analytica Chimica Acta, 2000, vol. 417, pp. 211-220. doi:10.1016/S0003-2670(00)00929-6.179. Gremaud G., Quaile S., Piantini U., Pfammatter E., Corvi C. Characterization of Swiss vineyards using isotopic data in combination with trace elements and classical parameters. Eur. Food Res. Technol., 2004, vol. 219, pp. 97-104. doi:10.1007/s00217-004-0919-0.180. Dutra S.V, Adami L, Marcon A.R, Carnieli G.J, Roani C.A, Spinelli F.R, Leonardelli S, Ducatti C, Moreira M.Z, Vanderlinde R. Determination of the geographical origin of Brazilian wines by isotope and mineral analysis. Analytical and Bioanalytical Chemistry, 2011, vol. 401, pp. 1571-1576. doi:10.1007/s00216-011-5181-2.181. Almeida C.M., Vasconcelos M.T.S.D. ICP-MS determination of strontium isotope ratio in wine in order to be used as a fingerprint of its regional origin. J. Anal. At. Spectrom., 2001, vol. 16, pp. 607-611. doi:10.1039/B100307K.182. Liu L., Cozzolino D., Cynkar W.U., Gishen M., Colby C.B. Geographic Classification of Spanish and Australian Tempranillo Red Wines by Visible and Near-Infrared Spectroscopy Combined with Multivariate Analysis. J. Agric. Food Chem., 2006, vol. 54, pp. 6754-6759. doi:10.1021/jf061528b.183. Brescia M.A, Kosir I.J, Caldarola V., Kidric J., Sacco A. Chemometric Classification of Apulian and Slovenian Wines Using 1H NMR and ICP-OES Together with HPICE Data. J. Agric. Food Chem., 2003, vol. 51, pp. 21-26. doi:10.1021/jf0206015.184. Adami L, Dutra S.V, Marcon A.R, Carnieli G.J, Roani C.A, Vanderlinde R. Geographic origin of southern Brazilian wines by carbon and oxygen isotope analyses // Rapid Communications in Mass Spectrometry. 2010, vol. 24, no. 20, pp. 2943-2948. doi:10.1002/rcm.4726.185. Dutra S.V., Adami L., Marcon A.R., Carnieli G.J., Roani C.A., Spinellia F.R., Leonardelli S., Vanderlinde R. Characterization of wines according the geographical origin by analysis of isotopes and minerals and the influence of harvest on the isotope values. Food Chemistry, 2013, vol. 141, no. 3, pp. 2148-2153. doi:10.1016/j.foodchem.2013.04.106.186. Kaunova A.A., Petrov V.I., Tsiupko, T.G., Tеmеrdashеv Z.A., Pеrеkotii V.V., Luk'ianov A.A. [Identification of wine provenance by ICP-AES multielement analysis], Journal of Analytical Chemistry, 2013, vol. 68, no. 9, pp. 917-922. doi:10.7868/S0044450213090065. ; Проведен анализ опубликованных работ и нормативных документов, посвященных вопросам контроля качества и региональной принадлежности вин. Рассмотрен химический состав винограда и изготавливаемой из него винодельческой продукции, показано его качественное и количественное изменение в процессе винификации, созревания и выдержки вин. Установлены основные группы соединений, содержания и соотношения которых определяют качественные характеристики вин, а также играют важную роль в формировании аромата и вкуса напитка. Обсуждены предпосылки развития рынка поддельной продукции и способы фальсификации вин. Проведен анализ научной литературы и нормативной базы, регламентирующей качество вин на территории России и стран Европейского союза, существующих подходов к определению их подлинности, указаны достоинства и недостатки. Обсуждены примеры использования различных критериев для установления натуральных и фальсифицированных вин, а также подходов их комплексной идентификации и создания системы оценки качества винодельческой продукции с помощью методов физико-химического анализа. Проанализированы основные методические подходы к установлению региональной принадлежности вин, сочетающие возможности современных методов анализа, математического моделирования и статистики, продемонстрированы примеры их использования на практике.Ключевые слова: вина, методы анализа, качество, подлинность, региональная принадлежность, фальсификация, математическое моделированиеDOI: http://dx.doi.org/10.15826/analitika.2014.18.4.001