04-2The combined action TVS mud index/TVS skin test as an evaluation marker of skin functionality and thermal mud effectiveness / 日本温泉気候物理医学会雑誌

<b>Introduction: </b>To evaluate the influence of the skin aging critical level on the development of objective thermal protocols, an improved integrated tensiometric approach was developed named as Tensiometric Versus Skin (TVS) modeling.<BR>  TVS modeling: (i) exploits the structure-surface correlations which are characteristic of all systems; (ii) applies the principle of permutability of the tensiometric technique, according to which unknown solids can be characterized by their known surface characteristics, and vice versa; (iii) is carried out in a non-invasive way by a tensiometric contact angle method.<BR>  TVS modeling involves TVS skin test as an objective evaluation marker of the epidermal functional state, and TVS mud index as an evaluation marker of thermal matrices.<BR><b>Objectives: </b>On the basis of these scientific evidences, the combined action of TVS mud index with TVS skin test was investigated to develop objective dose-response thermal protocols.<BR>  The first “OTP-TVS thermal protocol” was developed in the Euganean thermal area where fangotherapy is widely practiced.<BR><b>Materials and Methods: </b>Native Euganean thermal mud was firstly characterized from the chemical and mineralogical point of view. After maturation in controlled conditions, TVS mud index was obtained by contact angle method using PFPE as reference standard liquid, and finally, by repeated TVS skin test before and after a dose of fango application, the fango effectiveness was performed. <BR><b>Results: </b>The schematic OTP-TVS protocol pathway is shown in Figure 1.

04-11Quality assessment of Japanese Biofango through tensiometric approach by TVS mud index / 日本温泉気候物理医学会雑誌

<b>Introduction: </b>Sanraku-en spa started to purpose the “Shogawa biofangotherapy” using hot spring water and different kind of clays of natural origin (called Biofango) matured for three weeks during which bacterial flora develop with production of constitutive elements having therapeutic properties [4]. In collaboration with Ascendant Co. Ltd was ideated and developed the production of the first japanese Biofango supported by Toho University, University of Science and Technology of Hokuriku, and University of Hishigawa opening at new perspective in mudtherapy for therapeutic use in Japan (Biofango project).<BR><b>Objectives: </b>The goal was the assessing the surface energy of Biofango by TVS modelling and TVS mud index ^{1, 2)}. Tensiometric analyses of Biofango mixtures were performed at Sanraku-en spas centre (Tonami-Japan) and its quality control has been carried out in the Permanent Thermal Observatory (OTP) of University of Padova. Organic compounds analysis (TOC) were performed in the Department of Pharmaceutical and Pharmacological Sciences of University of Padova (Italy).<BR><b>Materials and Methods: </b>Biofango was prepared using KomatsuClay, MotoyamaClay, WakuraDiatomite and KasaokaBentonite. Pre-test mixtures were K01 (Bentonite 1.75, KomatsuClay 0.5, Diatomite 0.25) and M01 (Bentonite 1.75 MotoyamaClay 0.5 Diatomite 0.25). After were prepared K02 (Bentonite 1.25, Kaolinite 1.5, Diatomite 0.25) and A01 (KasaokaBentonite 1.25, Kaolinite 0.5, Diatomite 0.25) mixtures. Final Biofangos were BFM+0%Dolomite, MAT1+10%Dolomite, MAT2+18%Dolomite, and MAT3+35%Dolomite were analysed by XRF/XRD. TOC analyses were performed on a Perkin-Elmer-2400 analyser with Perkin-Elmer-AD-4 autobalance and tensiometric investigations were performed by DSA 10 (Krüss) tensiometer employing (a) PFPE, Fomblin HC/OH-1000, diiodomethane, glycerine as liquid tests and (b) Owens-Wendt³⁾ mathematical model to convert contact angles in surface enery parameters. <BR><b>Results: </b>XRD analyses of Biofango demonstrating presence of Kaolinite-Quartz-Feldspar in Komatsu Clay, Kaolinite-Quartz-Feldspar-Carbon in MotoyamaClay, Quartz-Montmorillonite-Feldspar-Grauconite in WakuraDiatomite, and Montmorillonite-Quartz-Feldspar-Christoballite in KasaokaBentonite while XRF showed presence of SiO₂ (KomatsuClay 53.38%, MotoyamaClay 48.86%, WakuraDiatomite 78.20%, KasaokaBentonite 66.01%) and Al₂O₃ (KomatsuClay 53.38%, MotoyamaClay 48.86%, WakuraDiatomite 78.20%, KasaokaBentonite 66.01%) as principal elements. TOC analyses demonstrated an increase of C% with production of CO₂ in relation to the amount of Dolomite in Biofango mixtures (MAT1=1.26%, MAT2=2.36%, MAT3=3.29%). Tensiometric investigations showed a correlation between C% and dispersed components (DC) measured on Biofango mixtures (MAT1=3.0 mN/m, MAT2=2.1 mN/m, MAT3=2.0 mN/m) and between C% and TVS mud index levels (MAT1=68.7 mN/m eq., MAT2=74.06 mN/m eq., MAT3=75.9 mN/m eq.).<BR><b>Conclusions:</b> Tensiometric investigations of Biofango consented to determine the correlations between chemico-mineralogical data and surface energy parameters. Thanking to the high sensitivity of TVS mud index used as integrated tensiometric marker was possible to determine directly and in a non invasive way the quality of Biofango mixtures opening at new perspective in their monitoring and control before their employment in mudtherapy in Japanese spas after their maturation process.

04-10Quality assessment of maturation process of Japanese Biofango by TVS mud index / 日本温泉気候物理医学会雑誌

<b>Introduction: </b>TVS mud index¹⁾ is a tensiometric marker for quality and maturation process control of Italian Euganean Thermal Muds (ETM) which sensitivity defined on objective basis their quality and maturation degree. <BR><b>Objectives: </b>The goal was to assess the maturation process of Biofango by TVS mud index (Sanraku-en spas centre, Japan and Osservatorio Termale Permanente-OTP, Italy), and its organic compounds by TOC analyses (University of Padova, Italy).<BR><b>Materials and Methods:</b> Biofango was prepared using KomatsuClay, MotoyamaClay, WakuraDiatomite and KasaokaBentonite giving K02 (Bentonite 1.25, Kaolinite 1.5, Diatomite 0.25) and A01 (KasaokaBentonite 1.25, Kaolinite 0.5, Diatomite 0.25). Final Biofango BFM+0%Dolomite, MAT1+10%Dolomite, MAT2+18%Dolomite, and MAT3+35%Dolomite were analyzed by TOC (Perkin-Elmer-2400) and DSA10-Krüss employing (a) PFPE, Fomblin HC/OH-1000, diiodomethane, glycerine as liquid tests and (b) Owens-Wendt mathematical model for conversion of contact angles in surface energy parameters²⁾.<BR><b>Results:</b> The behaviour of C(%) in MAT1, MAT2, and MAT3 during maturation process (20°C) showed respectively (a) MAT1t0h=1.26%, MAT1t216h=0.91%, MAT1t360=1.08%, MAT1t576h=1.23%, MAT1t720h=0.98%, (b) MAT2t0h=2.36%, MAT2t216h=1.80%, MAT2t360=1.49%, MAT2t576h=1.86%, MAT2t720h=1.68%, (c) MAT3t0h=3.29%, MAT3t216h=2.71%, MAT3t360=2.57%, MAT3t576h=2.6%, MAT3t720h=2.7%. C% decrease demonstrating the influence of Dolomite in Biofango mixtures. Dispersed energy components (DC) of MAT1, MAT2, and MAT3 showed respectively (a) MAT1t0h=3.0mN/m, MAT1t216h=3.1mN/m, MAT1t360=2.9mN/m, MAT1t576h=3.8mN/m, MAT1t720h=2.5mN/m, (b) MAT2t0h=2.1mN/m, MAT2t216h=2.2mN/m, MAT2t360=3.1mN/m, MAT2t576h=3.7mN/m, MAT2t720h=2.6mN/m, (c)MAT3t0h=2.0mN/m, MAT3t216h=2.6mN/m, MAT3t360=2.6mN/m, MAT3t576h=2.9mN/m, MAT2t720h=3.0mN/m. On the other side TVS mud index showed respectively (a) MAT1t0h=68.7mN/m, MAT1t216h=70.26mN/m, MAT1t360=71.78mN/m, MAT1t576h=64.69mN/m, MAT1t720h=71.84mN/m, (b) MAT2t0h=74.06mN/m, MAT2t216h=71.69mN/m, MAT2t360= 70.36mN/m, MAT2t576h=65.83mN/m, MAT2t720h=71.23mN/m, (c) MAT3t0h=75.9mN/m, MAT3t216h=73.05mN/m, MAT3t360=73.34mN/m, MAT3t576h=68.52mN/m, MAT3t720h=68.66mN/m proportionally inverse with DC behaviour. MAT3 with highest content in Dolomite demonstrated great capability to uptake DC during maturation process with consequently decrease of TVS mud index levels accordingly with TOC result.<BR><b>Conclusions: </b>Tensiometric investigations of Biofango underlined the links between chemical and surface energy data. The high sensitivity of TVS mud index consented to follow directly in a non invasive way the structural-surface changes in Biofango mixtures occurred during maturation process opening at new perspective for their control.

04-12Introduction to “TVS mud index” as an evaluation marker of silt-clayey matrices for bioadhesive thermal and cosmetic applications / 日本温泉気候物理医学会雑誌

<b>Introduction: </b>Brenta’s silt-clay consist of silt with clay containing Italian Dolomites minerals extracted from the catchment area of Brenta river. Sediments were investigated by SEM, XRD, XRF and particle size granulometer. The presence of SiO₂ (34.16%), CaO (17.12%), and Al2O3 (11.15%) as principal elements is comparable with the typical composition of Euganean Thermal Muds (ETM) of Euganean Thermal Area (ETA) which average level of SiO₂, CaO, and Al₂O₃ are respectively 38.75%, 17.74%, and 7.70%¹⁾. Tensiometric investigation of Brenta’s silt-clay were performed hypothesizing its employ in mudtherapy. <BR><b>Objectives:</b> Surface energy of natural ETM and its maturation process were monitored by TVS mud index, a tensiometric marker for the determination of the quality of a thermal mud²⁾. The aim of this work was to determine the quality of Brenta’s silt-clay by tensiometric approach introducing it in the field of thermalism.<BR><b>Materials and Methods: </b>Brenta’s silt-clayey (ie Brenta Ker) samples were collected from EGAP’s gravel pit, undergone at maturation process for 6 weeks employing thermal water, investigated using DSA10-Kruss tensiometer with diiodomethane, PFPE, glycerine as liquid tests. <BR>  Tensiometric characterizations were performed by measurement of contact angles (deg) of different liquid tests and their conversion in surface energy (mN/m) by Owens mathematical model ³⁾. TVS mud index levels were determined trough the measurements of contact angles of PFPE ⁴⁾ by Perfluoropolyether Contact Angle Measurement Method (PCAM) for maturation process (mN/m eq./weeks) and speed (m*Nm^-1/h) evaluations. <BR><b>Results: </b>The correlation degree between ETM XRF elements data (ppm) and those of Brenta’s silt-clay (ppm) was satisfactory (R2=0.82) confirming the common origin of two kind of matrices. Considering 6 weeks of maturation, surface energy profile of Brenta’s silt-clay, expressed as dispersed component (DC) and polar component (PC), showed respectively 17.84 mN/m and 32.04 mN/m with coefficients of variations (CV%) around 22.43% and 14.29%. TVS mud index levels monitored during maturation process showed a clear decrease in the time (t0=84.02.5 mN/m eq, t1=71.01.9 mN/m eq., t2=79.80.7 mN/m eq., t3=72.63.1 mN/m eq., t4=61.22.6 mN/m eq., t5=65.12.1 mN/m eq., t6=58.81.6 mN/m eq.) underlined by the decrease of maturation speed monitored for 60 days and expressed as DC per hour (t48=0.08 m*Nm^-1/h, t120=0.03 m*Nm^-1/h, t144=0.04 m*Nm^-1/h, t384= 0.02 m*Nm^-1/h, t1416=0.005 m*Nm^-1/h).<BR><b>Conclusions: </b>Tensiometric investigations by TVS modelling and maturation speed evaluations confirmed the suitability of Brenta’s silt-clay to be employed in thermal field opening new perspectives in mudtherapy.

04-12 Introduction to “TVS mud index” as an evaluation marker of silt-clayey matrices for bioadhesive thermal and cosmetic applications / 日本温泉気候物理医学会雑誌

Introduction: Brenta’s silt-clay consist of silt with clay containing Italian Dolomites minerals extracted from the catchment area of Brenta river. Sediments were investigated by SEM, XRD, XRF and particle size granulometer. The presence of SiO2 (34.16%), CaO (17.12%), and Al2O3 (11.15%) as principal elements is comparable with the typical composition of Euganean Thermal Muds (ETM) of Euganean Thermal Area (ETA) which average level of SiO2, CaO, and Al2O3 are respectively 38.75%, 17.74%, and 7.70%1). Tensiometric investigation of Brenta’s silt-clay were performed hypothesizing its employ in mudtherapy. Objectives: Surface energy of natural ETM and its maturation process were monitored by TVS mud index, a tensiometric marker for the determination of the quality of a thermal mud2). The aim of this work was to determine the quality of Brenta’s silt-clay by tensiometric approach introducing it in the field of thermalism. Materials and Methods: Brenta’s silt-clayey (ie Brenta Ker) samples were collected from EGAP’s gravel pit, undergone at maturation process for 6 weeks employing thermal water, investigated using DSA10-Kruss tensiometer with diiodomethane, PFPE, glycerine as liquid tests.   Tensiometric characterizations were performed by measurement of contact angles (deg) of different liquid tests and their conversion in surface energy (mN/m) by Owens mathematical model 3). TVS mud index levels were determined trough the measurements of contact angles of PFPE 4) by Perfluoropolyether Contact Angle Measurement Method (PCAM) for maturation process (mN/m eq./weeks) and speed (m*Nm-1/h) evaluations. Results: The correlation degree between ETM XRF elements data (ppm) and those of Brenta’s silt-clay (ppm) was satisfactory (R2=0.82) confirming the common origin of two kind of matrices. Considering 6 weeks of maturation, surface energy profile of Brenta’s silt-clay, expressed as dispersed component (DC) and polar component (PC), showed respectively 17.84 mN/m and 32.04 mN/m with coefficients of variations (CV%) around 22.43% and 14.29%. TVS mud index levels monitored during maturation process showed a clear decrease in the time (t0=84.02.5 mN/m eq, t1=71.01.9 mN/m eq., t2=79.80.7 mN/m eq., t3=72.63.1 mN/m eq., t4=61.22.6 mN/m eq., t5=65.12.1 mN/m eq., t6=58.81.6 mN/m eq.) underlined by the decrease of maturation speed monitored for 60 days and expressed as DC per hour (t48=0.08 m*Nm-1/h, t120=0.03 m*Nm-1/h, t144=0.04 m*Nm-1/h, t384= 0.02 m*Nm-1/h, t1416=0.005 m*Nm-1/h). Conclusions: Tensiometric investigations by TVS modelling and maturation speed evaluations confirmed the suitability of Brenta’s silt-clay to be employed in thermal field opening new perspectives in mudtherapy.

04-11 Quality assessment of Japanese Biofango through tensiometric approach by TVS mud index / 日本温泉気候物理医学会雑誌

Introduction: Sanraku-en spa started to purpose the “Shogawa biofangotherapy” using hot spring water and different kind of clays of natural origin (called Biofango) matured for three weeks during which bacterial flora develop with production of constitutive elements having therapeutic properties [4]. In collaboration with Ascendant Co. Ltd was ideated and developed the production of the first japanese Biofango supported by Toho University, University of Science and Technology of Hokuriku, and University of Hishigawa opening at new perspective in mudtherapy for therapeutic use in Japan (Biofango project). Objectives: The goal was the assessing the surface energy of Biofango by TVS modelling and TVS mud index 1, 2). Tensiometric analyses of Biofango mixtures were performed at Sanraku-en spas centre (Tonami-Japan) and its quality control has been carried out in the Permanent Thermal Observatory (OTP) of University of Padova. Organic compounds analysis (TOC) were performed in the Department of Pharmaceutical and Pharmacological Sciences of University of Padova (Italy). Materials and Methods: Biofango was prepared using KomatsuClay, MotoyamaClay, WakuraDiatomite and KasaokaBentonite. Pre-test mixtures were K01 (Bentonite 1.75, KomatsuClay 0.5, Diatomite 0.25) and M01 (Bentonite 1.75 MotoyamaClay 0.5 Diatomite 0.25). After were prepared K02 (Bentonite 1.25, Kaolinite 1.5, Diatomite 0.25) and A01 (KasaokaBentonite 1.25, Kaolinite 0.5, Diatomite 0.25) mixtures. Final Biofangos were BFM+0%Dolomite, MAT1+10%Dolomite, MAT2+18%Dolomite, and MAT3+35%Dolomite were analysed by XRF/XRD. TOC analyses were performed on a Perkin-Elmer-2400 analyser with Perkin-Elmer-AD-4 autobalance and tensiometric investigations were performed by DSA 10 (Krüss) tensiometer employing (a) PFPE, Fomblin HC/OH-1000, diiodomethane, glycerine as liquid tests and (b) Owens-Wendt3) mathematical model to convert contact angles in surface enery parameters. Results: XRD analyses of Biofango demonstrating presence of Kaolinite-Quartz-Feldspar in Komatsu Clay, Kaolinite-Quartz-Feldspar-Carbon in MotoyamaClay, Quartz-Montmorillonite-Feldspar-Grauconite in WakuraDiatomite, and Montmorillonite-Quartz-Feldspar-Christoballite in KasaokaBentonite while XRF showed presence of SiO2 (KomatsuClay 53.38%, MotoyamaClay 48.86%, WakuraDiatomite 78.20%, KasaokaBentonite 66.01%) and Al2O3 (KomatsuClay 53.38%, MotoyamaClay 48.86%, WakuraDiatomite 78.20%, KasaokaBentonite 66.01%) as principal elements. TOC analyses demonstrated an increase of C% with production of CO2 in relation to the amount of Dolomite in Biofango mixtures (MAT1=1.26%, MAT2=2.36%, MAT3=3.29%). Tensiometric investigations showed a correlation between C% and dispersed components (DC) measured on Biofango mixtures (MAT1=3.0 mN/m, MAT2=2.1 mN/m, MAT3=2.0 mN/m) and between C% and TVS mud index levels (MAT1=68.7 mN/m eq., MAT2=74.06 mN/m eq., MAT3=75.9 mN/m eq.). Conclusions: Tensiometric investigations of Biofango consented to determine the correlations between chemico-mineralogical data and surface energy parameters. Thanking to the high sensitivity of TVS mud index used as integrated tensiometric marker was possible to determine directly and in a non invasive way the quality of Biofango mixtures opening at new perspective in their monitoring and control before their employment in mudtherapy in Japanese spas after their maturation process.

04-10 Quality assessment of maturation process of Japanese Biofango by TVS mud index / 日本温泉気候物理医学会雑誌

Introduction: TVS mud index1) is a tensiometric marker for quality and maturation process control of Italian Euganean Thermal Muds (ETM) which sensitivity defined on objective basis their quality and maturation degree. Objectives: The goal was to assess the maturation process of Biofango by TVS mud index (Sanraku-en spas centre, Japan and Osservatorio Termale Permanente-OTP, Italy), and its organic compounds by TOC analyses (University of Padova, Italy). Materials and Methods: Biofango was prepared using KomatsuClay, MotoyamaClay, WakuraDiatomite and KasaokaBentonite giving K02 (Bentonite 1.25, Kaolinite 1.5, Diatomite 0.25) and A01 (KasaokaBentonite 1.25, Kaolinite 0.5, Diatomite 0.25). Final Biofango BFM+0%Dolomite, MAT1+10%Dolomite, MAT2+18%Dolomite, and MAT3+35%Dolomite were analyzed by TOC (Perkin-Elmer-2400) and DSA10-Krüss employing (a) PFPE, Fomblin HC/OH-1000, diiodomethane, glycerine as liquid tests and (b) Owens-Wendt mathematical model for conversion of contact angles in surface energy parameters2). Results: The behaviour of C(%) in MAT1, MAT2, and MAT3 during maturation process (20°C) showed respectively (a) MAT1t0h=1.26%, MAT1t216h=0.91%, MAT1t360=1.08%, MAT1t576h=1.23%, MAT1t720h=0.98%, (b) MAT2t0h=2.36%, MAT2t216h=1.80%, MAT2t360=1.49%, MAT2t576h=1.86%, MAT2t720h=1.68%, (c) MAT3t0h=3.29%, MAT3t216h=2.71%, MAT3t360=2.57%, MAT3t576h=2.6%, MAT3t720h=2.7%. C% decrease demonstrating the influence of Dolomite in Biofango mixtures. Dispersed energy components (DC) of MAT1, MAT2, and MAT3 showed respectively (a) MAT1t0h=3.0mN/m, MAT1t216h=3.1mN/m, MAT1t360=2.9mN/m, MAT1t576h=3.8mN/m, MAT1t720h=2.5mN/m, (b) MAT2t0h=2.1mN/m, MAT2t216h=2.2mN/m, MAT2t360=3.1mN/m, MAT2t576h=3.7mN/m, MAT2t720h=2.6mN/m, (c)MAT3t0h=2.0mN/m, MAT3t216h=2.6mN/m, MAT3t360=2.6mN/m, MAT3t576h=2.9mN/m, MAT2t720h=3.0mN/m. On the other side TVS mud index showed respectively (a) MAT1t0h=68.7mN/m, MAT1t216h=70.26mN/m, MAT1t360=71.78mN/m, MAT1t576h=64.69mN/m, MAT1t720h=71.84mN/m, (b) MAT2t0h=74.06mN/m, MAT2t216h=71.69mN/m, MAT2t360= 70.36mN/m, MAT2t576h=65.83mN/m, MAT2t720h=71.23mN/m, (c) MAT3t0h=75.9mN/m, MAT3t216h=73.05mN/m, MAT3t360=73.34mN/m, MAT3t576h=68.52mN/m, MAT3t720h=68.66mN/m proportionally inverse with DC behaviour. MAT3 with highest content in Dolomite demonstrated great capability to uptake DC during maturation process with consequently decrease of TVS mud index levels accordingly with TOC result. Conclusions: Tensiometric investigations of Biofango underlined the links between chemical and surface energy data. The high sensitivity of TVS mud index consented to follow directly in a non invasive way the structural-surface changes in Biofango mixtures occurred during maturation process opening at new perspective for their control.

04-2 The combined action TVS mud index/TVS skin test as an evaluation marker of skin functionality and thermal mud effectiveness / 日本温泉気候物理医学会雑誌

Introduction: To evaluate the influence of the skin aging critical level on the development of objective thermal protocols, an improved integrated tensiometric approach was developed named as Tensiometric Versus Skin (TVS) modeling.   TVS modeling: (i) exploits the structure-surface correlations which are characteristic of all systems; (ii) applies the principle of permutability of the tensiometric technique, according to which unknown solids can be characterized by their known surface characteristics, and vice versa; (iii) is carried out in a non-invasive way by a tensiometric contact angle method.   TVS modeling involves TVS skin test as an objective evaluation marker of the epidermal functional state, and TVS mud index as an evaluation marker of thermal matrices. Objectives: On the basis of these scientific evidences, the combined action of TVS mud index with TVS skin test was investigated to develop objective dose-response thermal protocols.   The first “OTP-TVS thermal protocol” was developed in the Euganean thermal area where fangotherapy is widely practiced. Materials and Methods: Native Euganean thermal mud was firstly characterized from the chemical and mineralogical point of view. After maturation in controlled conditions, TVS mud index was obtained by contact angle method using PFPE as reference standard liquid, and finally, by repeated TVS skin test before and after a dose of fango application, the fango effectiveness was performed. Results: The schematic OTP-TVS protocol pathway is shown in Figure 1.