Search results for: WDXRF spectrometer
Commenced in January 2007
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Edition: International
Paper Count: 229

Search results for: WDXRF spectrometer

19 Aerosol Chemical Composition in Urban Sites: A Comparative Study of Lima and Medellin

Authors: Guilherme M. Pereira, Kimmo Teinïla, Danilo Custódio, Risto Hillamo, Célia Alves, Pérola de C. Vasconcellos

Abstract:

South American large cities often present serious air pollution problems and their atmosphere composition is influenced by a variety of emissions sources. The South American Emissions Megacities, and Climate project (SAEMC) has focused on the study of emissions and its influence on climate in the South American largest cities and it also included Lima (Peru) and Medellin (Colombia), sites where few studies of the genre were done. Lima is a coastal city with more than 8 million inhabitants and the second largest city in South America. Medellin is a 2.5 million inhabitants city and second largest city in Colombia; it is situated in a valley. The samples were collected in quartz fiber filters in high volume samplers (Hi-Vol), in 24 hours of sampling. The samples were collected in intensive campaigns in both sites, in July, 2010. Several species were determined in the aerosol samples of Lima and Medellin. Organic and elemental carbon (OC and EC) in thermal-optical analysis; biomass burning tracers (levoglucosan - Lev, mannosan - Man and galactosan - Gal) in high-performance anion exchange ion chromatography with mass spectrometer detection; water soluble ions in ion chromatography. The average particulate matter was similar for both campaigns, the PM10 concentrations were above the recommended by World Health Organization (50 µg m⁻³ – daily limit) in 40% of the samples in Medellin, while in Lima it was above that value in 15% of the samples. The average total ions concentration was higher in Lima (17450 ng m⁻³ in Lima and 3816 ng m⁻³ in Medellin) and the average concentrations of sodium and chloride were higher in this site, these species also had better correlations (Pearson’s coefficient = 0,63); suggesting a higher influence of marine aerosol in the site due its location in the coast. Sulphate concentrations were also much higher at Lima site; which may be explained by a higher influence of marine originated sulphate. However, the OC, EC and monosaccharides average concentrations were higher at Medellin site; this may be due to the lower dispersion of pollutants due to the site’s location and a larger influence of biomass burning sources. The levoglucosan average concentration was 95 ng m⁻³ for Medellin and 16 ng m⁻³ and OC was well correlated with levoglucosan (Pearson’s coefficient = 0,86) in Medellin; suggesting a higher influence of biomass burning over the organic aerosol in this site. The Lev/Man ratio is often related to the type of biomass burned and was close to 18, similar to the observed in previous studies done at biomass burning impacted sites in the Amazon region; backward trajectories also suggested the transport of aerosol from that region. Biomass burning appears to have a larger influence on the air quality in Medellin, in addition the vehicular emissions; while Lima showed a larger influence of marine aerosol during the study period.

Keywords: aerosol transport, atmospheric particulate matter, biomass burning, SAEMC project

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18 Storage of Organic Carbon in Chemical Fractions in Acid Soil as Influenced by Different Liming

Authors: Ieva Jokubauskaite, Alvyra Slepetiene, Danute Karcauskiene, Inga Liaudanskiene, Kristina Amaleviciute

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Soil organic carbon (SOC) is the key soil quality and ecological stability indicator, therefore, carbon accumulation in stable forms not only supports and increases the organic matter content in the soil, but also has a positive effect on the quality of soil and the whole ecosystem. Soil liming is one of the most common ways to improve the carbon sequestration in the soil. Determination of the optimum intensity and combinations of liming in order to ensure the optimal carbon quantitative and qualitative parameters is one of the most important tasks of this work. The field experiments were carried out at the Vezaiciai Branch of Lithuanian Research Centre for Agriculture and Forestry (LRCAF) during the 2011–2013 period. The effect of liming with different intensity (at a rate 0.5 every 7 years and 2.0 every 3-4 years) was investigated in the topsoil of acid moraine loam Bathygleyic Dystric Glossic Retisol. Chemical analyses were carried out at the Chemical Research Laboratory of Institute of Agriculture, LRCAF. Soil samples for chemical analyses were taken from the topsoil after harvesting. SOC was determined by the Tyurin method modified by Nikitin, measuring with spectrometer Cary 50 (VARIAN) at 590 nm wavelength using glucose standards. SOC fractional composition was determined by Ponomareva and Plotnikova version of classical Tyurin method. Dissolved organic carbon (DOC) was analyzed using an ion chromatograph SKALAR in water extract at soil-water ratio 1:5. Spectral properties (E4/E6 ratio) of humic acids were determined by measuring the absorbance of humic and fulvic acids solutions at 465 and 665 nm. Our study showed a negative statistically significant effect of periodical liming (at 0.5 and 2.0 liming rates) on SOC content in the soil. The content of SOC was 1.45% in the unlimed treatment, while in periodically limed at 2.0 liming rate every 3–4 years it was approximately by 0.18 percentage points lower. It was revealed that liming significantly decreased the DOC concentration in the soil. The lowest concentration of DOC (0.156 g kg-1) was established in the most intensively limed (2.0 liming rate every 3–4 years) treatment. Soil liming exerted an increase of all humic acids and fulvic acid bounded with calcium fractions content in the topsoil. Soil liming resulted in the accumulation of valuable humic acids. Due to the applied liming, the HR/FR ratio, indicating the quality of humus increased to 1.08 compared with that in unlimed soil (0.81). Intensive soil liming promoted the formation of humic acids in which groups of carboxylic and phenolic compounds predominated. These humic acids are characterized by a higher degree of condensation of aromatic compounds and in this way determine the intensive organic matter humification processes in the soil. The results of this research provide us with the clear information on the characteristics of SOC change, which could be very useful to guide the climate policy and sustainable soil management.

Keywords: acid soil, carbon sequestration, long–term liming, soil organic carbon

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17 Characterization of Alloyed Grey Cast Iron Quenched and Tempered for a Smooth Roll Application

Authors: Mohamed Habireche, Nacer E. Bacha, Mohamed Djeghdjough

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In the brick industry, smooth double roll crusher is used for medium and fine crushing of soft to medium hard material. Due to opposite inward rotation of the rolls, the feed material is nipped between the rolls and crushed by compression. They are subject to intense wear, known as three-body abrasion, due to the action of abrasive products. The production downtime affecting productivity stems from two sources: the bi-monthly rectification of the roll crushers and their replacement when they are completely worn out. Choosing the right material for the roll crushers should result in longer machine cycles, and reduced repair and maintenance costs. All roll crushers are imported from outside Algeria. This results in sometimes very long delivery times which handicap the brickyards, in particular in respecting delivery times and honored the orders made by customers. The aim of this work is to investigate the effect of alloying additions on microstructure and wear behavior of grey lamellar cast iron for smooth roll crushers in brick industry. The base gray iron was melted in an induction furnace with low frequency at a temperature of 1500 °C, in which return cast iron scrap, new cast iron ingot, and steel scrap were added to the melt to generate the desired composition. The chemical analysis of the bar samples was carried out using Emission Spectrometer Systems PV 8050 Series (Philips) except for the carbon, for which a carbon/sulphur analyser Elementrac CS-i was used. Unetched microstructure was used to evaluate the graphite flake morphology using the image comparison measurement method. At least five different fields were selected for quantitative estimation of phase constituents. The samples were observed under X100 magnification with a Zeiss Axiover T40 MAT optical microscope equipped with a digital camera. SEM microscope equipped with EDS was used to characterize the phases present in the microstructure. The hardness (750 kg load, 5mm diameter ball) was measured with a Brinell testing machine for both treated and as-solidified condition test pieces. The test bars were used for tensile strength and metallographic evaluations. Mechanical properties were evaluated using tensile specimens made as per ASTM E8 standards. Two specimens were tested for each alloy. From each rod, a test piece was made for the tensile test. The results showed that the quenched and tempered alloys had best wear resistance at 400 °C for alloyed grey cast iron (containing 0.62%Mn, 0.68%Cr, and 1.09% Cu) due to fine carbides in the tempered matrix. In quenched and tempered condition, increasing Cu content in cast irons improved its wear resistance moderately. Combined addition of Cu and Cr increases hardness and wear resistance for a quenched and tempered hypoeutectic grey cast iron.

Keywords: casting, cast iron, microstructure, heat treating

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16 Application of Laser-Induced Breakdown Spectroscopy for the Evaluation of Concrete on the Construction Site and in the Laboratory

Authors: Gerd Wilsch, Tobias Guenther, Tobias Voelker

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In view of the ageing of vital infrastructure facilities, a reliable condition assessment of concrete structures is becoming of increasing interest for asset owners to plan timely and appropriate maintenance and repair interventions. For concrete structures, reinforcement corrosion induced by penetrating chlorides is the dominant deterioration mechanism affecting the serviceability and, eventually, structural performance. The determination of the quantitative chloride ingress is required not only to provide valuable information on the present condition of a structure, but the data obtained can also be used for the prediction of its future development and associated risks. At present, wet chemical analysis of ground concrete samples by a laboratory is the most common test procedure for the determination of the chloride content. As the chloride content is expressed by the mass of the binder, the analysis should involve determination of both the amount of binder and the amount of chloride contained in a concrete sample. This procedure is laborious, time-consuming, and costly. The chloride profile obtained is based on depth intervals of 10 mm. LIBS is an economically viable alternative providing chloride contents at depth intervals of 1 mm or less. It provides two-dimensional maps of quantitative element distributions and can locate spots of higher concentrations like in a crack. The results are correlated directly to the mass of the binder, and it can be applied on-site to deliver instantaneous results for the evaluation of the structure. Examples for the application of the method in the laboratory for the investigation of diffusion and migration of chlorides, sulfates, and alkalis are presented. An example for the visualization of the Li transport in concrete is also shown. These examples show the potential of the method for a fast, reliable, and automated two-dimensional investigation of transport processes. Due to the better spatial resolution, more accurate input parameters for model calculations are determined. By the simultaneous detection of elements such as carbon, chlorine, sodium, and potassium, the mutual influence of the different processes can be determined in only one measurement. Furthermore, the application of a mobile LIBS system in a parking garage is demonstrated. It uses a diode-pumped low energy laser (3 mJ, 1.5 ns, 100 Hz) and a compact NIR spectrometer. A portable scanner allows a two-dimensional quantitative element mapping. Results show the quantitative chloride analysis on wall and floor surfaces. To determine the 2-D distribution of harmful elements (Cl, C), concrete cores were drilled, split, and analyzed directly on-site. Results obtained were compared and verified with laboratory measurements. The results presented show that the LIBS method is a valuable addition to the standard procedures - the wet chemical analysis of ground concrete samples. Currently, work is underway to develop a technical code of practice for the application of the method for the determination of chloride concentration in concrete.

Keywords: chemical analysis, concrete, LIBS, spectroscopy

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15 Raman Spectroscopy of Fossil-like Feature in Sooke #1 from Vancouver Island

Authors: J. A. Sawicki, C. Ebrahimi

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The first geochemical, petrological, X-ray diffraction, Raman, Mössbauer, and oxygen isotopic analyses of very intriguing 13-kg Sooke #1 stone covered in 70% of its surface with black fusion crust, found in and recovered from Sooke Basin, near Juan de Fuca Strait, in British Columbia, were reported as poster #2775 at LPSC52 in March. Our further analyses reported in poster #6305 at 84AMMS in August and comparisons with the Mössbauer spectra of Martian meteorite MIL03346 and Martian rocks in Gusev Crater reported by Morris et al. suggest that Sooke #1 find could be a stony achondrite of Martian polymict breccia type ejected from early watery Mars. Here, the Raman spectra of a carbon-rich ~1-mm² fossil-like white area identified in this rock on a surface of polished cut have been examined in more detail. The low-intensity 532 nm and 633 nm beams of the InviaRenishaw microscope were used to avoid any destructive effects. The beam was focused through the microscope objective to a 2 m spot on a sample, and backscattered light collected through this objective was recorded with CCD detector. Raman spectra of dark areas outside fossil have shown bands of clinopyroxene at 320, 660, and 1020 cm-1 and small peaks of forsteritic olivine at 820-840 cm-1, in agreement with results of X-ray diffraction and Mössbauer analyses. Raman spectra of the white area showed the broad band D at ~1310 cm-1 consisting of main mode A1g at 1305 cm⁻¹, E2g mode at 1245 cm⁻¹, and E1g mode at 1355 cm⁻¹ due to stretching diamond-like sp3 bonds in diamond polytype lonsdaleite, as in Ovsyuk et al. study. The band near 1600 cm-1 mostly consists of D2 band at 1620 cm-1 and not of the narrower G band at 1583 cm⁻¹ due to E2g stretching in planar sp2 bonds that are fundamental building blocks of carbon allotropes graphite and graphene. In addition, the broad second-order Raman bands were observed with 532 nm beam at 2150, ~2340, ~2500, 2650, 2800, 2970, 3140, and ~3300 cm⁻¹ shifts. Second-order bands in diamond and other carbon structures are ascribed to the combinations of bands observed in the first-order region: here 2650 cm⁻¹ as 2D, 2970 cm⁻¹ as D+G, and 3140 cm⁻¹ as 2G ones. Nanodiamonds are abundant in the Universe, found in meteorites, interplanetary dust particles, comets, and carbon-rich stars. The diamonds in meteorites are presently intensely investigated using Raman spectroscopy. Such particles can be formed by CVD process and during major impact shocks at ~1000-2300 K and ~30-40 GPa. It cannot be excluded that the fossil discovered in Sooke #1 could be a remnant of an alien carbon organism that transformed under shock impact to nanodiamonds. We trust that for the benefit of research in astro-bio-geology of meteorites, asteroids, Martian rocks, and soil, this find deserves further, more thorough investigations. If possible, the Raman SHERLOCK spectrometer operating on the Perseverance Rover should also search for such objects in the Martian rocks.

Keywords: achondrite, nanodiamonds, lonsdaleite, raman spectra

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14 Development of Biosensor Chip for Detection of Specific Antibodies to HSV-1

Authors: Zatovska T. V., Nesterova N. V., Baranova G. V., Zagorodnya S. D.

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In recent years, biosensor technologies based on the phenomenon of surface plasmon resonance (SPR) are becoming increasingly used in biology and medicine. Their application facilitates exploration in real time progress of binding of biomolecules and identification of agents that specifically interact with biologically active substances immobilized on the biosensor surface (biochips). Special attention is paid to the use of Biosensor analysis in determining the antibody-antigen interaction in the diagnostics of diseases caused by viruses and bacteria. According to WHO, the diseases that are caused by the herpes simplex virus (HSV), take second place (15.8%) after influenza as a cause of death from viral infections. Current diagnostics of HSV infection include PCR and ELISA assays. The latter allows determination the degree of immune response to viral infection and respective stages of its progress. In this regard, the searches for new and available diagnostic methods are very important. This work was aimed to develop Biosensor chip for detection of specific antibodies to HSV-1 in the human blood serum. The proteins of HSV1 (strain US) were used as antigens. The viral particles were accumulated in cell culture MDBK and purified by differential centrifugation in cesium chloride density gradient. Analysis of the HSV1 proteins was performed by polyacrylamide gel electrophoresis and ELISA. The protein concentration was measured using De Novix DS-11 spectrophotometer. The device for detection of antigen-antibody interactions was an optoelectronic two-channel spectrometer ‘Plasmon-6’, using the SPR phenomenon in the Krechman optical configuration. It was developed at the Lashkarev Institute of Semiconductor Physics of NASU. The used carrier was a glass plate covered with 45 nm gold film. Screening of human blood serums was performed using the test system ‘HSV-1 IgG ELISA’ (GenWay, USA). Development of Biosensor chip included optimization of conditions of viral antigen sorption and analysis steps. For immobilization of viral proteins 0.2% solution of Dextran 17, 200 (Sigma, USA) was used. Sorption of antigen took place at 4-8°C within 18-24 hours. After washing of chip, three times with citrate buffer (pH 5,0) 1% solution of BSA was applied to block the sites not occupied by viral antigen. It was found direct dependence between the amount of immobilized HSV1 antigen and SPR response. Using obtained biochips, panels of 25 positive and 10 negative for the content of antibodies to HSV-1 human sera were analyzed. The average value of SPR response was 185 a.s. for negative sera and from 312 to. 1264 a.s. for positive sera. It was shown that SPR data were agreed with ELISA results in 96% of samples proving the great potential of SPR in such researches. It was investigated the possibility of biochip regeneration and it was shown that application of 10 mM NaOH solution leads to rupture of intermolecular bonds. This allows reuse the chip several times. Thus, in this study biosensor chip for detection of specific antibodies to HSV1 was successfully developed expanding a range of diagnostic methods for this pathogen.

Keywords: biochip, herpes virus, SPR

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13 The Stable Isotopic Composition of Pedogenic Carbonate in the Minusinsk Basin, South Siberia

Authors: Jessica Vasil'chuk, Elena Ivanova, Pavel Krechetov, Vladimir Litvinsky, Nadine Budantseva, Julia Chizhova, Yurij Vasil'chuk

Abstract:

Carbonate minerals’ isotopic composition is widely used as a proxy for environmental parameters of the past. Pedogenic carbonate coatings on lower surfaces of coarse rock fragments are studied in order to indicate the climatic conditions and predominant vegetation under which they were formed. The purpose of the research is to characterize the isotopic composition of carbonate pedofeatures in soils of Minusink Hollow and estimate its correlation with isotopic composition of soil pore water, precipitation, vegetation and parent material. The samples of pedogenic carbonates, vegetation, carbonate parent material, soil water and precipitation water were analyzed using the Delta-V mass spectrometer with options of a gas bench and element analyser. The soils we studied are mainly Kastanozems that are poorly moisturized, therefore soil pore water was extracted by ethanol. Oxygen and carbon isotopic composition of pedogenic carbonates was analyzed in 3 key sites. Kazanovka Khakass state national reserve, Hankul salt lake, region of Sayanogorsk aluminum smelter. Vegetation photosynthetic pathway in the region is mainly C3. δ18O values of carbonate coatings in soils of Kazanovka vary in a range from −7.49 to −10.5‰ (vs V-PDB), and the smallest value −13.9‰ corresponds the coatings found between two buried soil horizons which 14C dates are 4.6 and 5.2 kyr BP. That may indicate cooler conditions of late Holocene than nowadays. In Sayanogorsk carbonates’ δ18O range is from −8.3 to −11.1‰ and near the Hankul Lake is from −9.0 to −10.2‰ all ranges are quite similar and may indicate coatings’ uniform formation conditions. δ13C values of carbonate coatings in Kazanovka vary from −2.5 to −6.7‰, the highest values correspond to the soils of Askiz and Syglygkug rivers former floodplains. For Sayanogorsk the range is from −4.9 to −6.8‰ and for Hankul from −2.3 to −5.7‰, where the highest value is for the modern salt crust. δ13C values of coatings strongly decrease from inner (older) to outer (younger) layers of coatings, that can indicate differences connected with the diffusion of organic material. Carbonate parent material δ18O value in the region vary from −11.1 to −12.0‰ and δ13C values vary from −4.9 to −5.7‰. Soil pore water δ18O values that determine the oxygen isotope composition of carbonates vary due to the processes of transpiration and mixing in the studied sites in a wide range of −2.0 to −13.5‰ (vs V-SMOW). Precipitation waters show δ18O values from -6.6‰ in May and -19.0‰ in January (snow) due to the temperature difference. The main conclusions are as follows: pedogenic carbonates δ13C values (−7…−2,5‰) show no correlation with modern C3 vegetation δ13C values (−30…−26‰), expected values under such vegetation are (−19…−15‰) but are closer to C4 vegetation. Late Holocene climate for the Minusinsk Hollow according to obtained data on isotope composition of carbonates and soil pore water chemical composition was dryer and cooler than present, that does not contradict with paleocarpology data obtained for the region. The research was supported by Russian Science Foundation (grant №14-27-00083).

Keywords: carbon, oxygen, pedogenic carbonates, South Siberia, stable isotopes

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12 Detection of Antibiotic Resistance Genes and Antibiotic Residues in Plant-based Products

Authors: Morello Sara, Pederiva Sabina, Bianchi Manila, Martucci Francesca, Marchis Daniela, Decastelli Lucia

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Vegetables represent an integral part of a healthy diet due to their valuable nutritional properties and the growth in consumer demand in recent years is particularly remarkable for a diet rich in vitamins and micronutrients. However, plant-based products are involved in several food outbreaks connected to various sources of contamination and quite often, bacteria responsible for side effects showed high resistance to antibiotics. The abuse of antibiotics can be one of the main mechanisms responsible for increasing antibiotic resistance (AR). Plants grown for food use can be contaminated directly by spraying antibiotics on crops or indirectly by treatments with antibiotics due to the use of manure, which may contain both antibiotics and genes of antibiotic resistance (ARG). Antibiotic residues could represent a potential way of human health risk due to exposure through the consumption of plant-based foods. The presence of antibiotic-resistant bacteria might pose a particular risk to consumers. The present work aims to investigate through a multidisciplinary approach the occurrence of ARG by means of a biomolecular approach (PCR) and the prevalence of antibiotic residues using a multi residues LC-MS/MS method, both in different plant-based products. During the period from July 2020 to October 2021, a total of 74 plant samples (33 lettuces and 41 tomatoes) were collected from 57 farms located throughout the Piedmont area, and18 out of 74 samples (11 lettuces and 7 tomatoes) were selected to LC-MS/MS analyses. DNA extracted (ExtractME, Blirt, Poland) from plants used on crops and isolated bacteria were analyzed with 6 sets of end-point multiplex PCR (Qiagen, Germany) to detect the presence of resistance genes of the main antibiotic families, such as tet genes (tetracyclines), bla (β-lactams) and mcr (colistin). Simultaneous detection of 43 molecules of antibiotics belonging to 10 different classes (tetracyclines, sulphonamides, quinolones, penicillins, amphenicols, macrolides, pleuromotilines, lincosamides, diaminopyrimidines) was performed using Exion LC system AB SCIEX coupled to a triple quadrupole mass spectrometer QTRAP 5500 from AB SCIEX. The PCR assays showed the presence of ARG in 57% (n=42): tetB (4.8%; n=2), tetA (9.5%; n=4), tetE (2.4%; n=1), tetL (12%; n=5), tetM (26%; n=11), blaSHV (21.5%; n=9), blaTEM (4.8%; n =2) and blaCTX-M (19%; n=8). In none of the analyzed samples was the mcr gene responsible for colistin resistance detected. Results obtained from LC-MS/MS analyses showed that none of the tested antibiotics appear to exceed the LOQ (100 ppb). Data obtained confirmed the presence of bacterial populations containing antibiotic resistance determinants such as tet gene (tetracycline) and bla genes (beta-lactams), widely used in human medicine, which can join the food chain and represent a risk for consumers, especially with raw products. The presence of traces of antibiotic residues in vegetables, in concentration below the LOQ of the LC-MS/MS method applied, cannot be excluded. In conclusion, traces of antibiotic residues could be a health risk to the consumer due to potential involvement in the spread of AR. PCR represents a useful and effective approach to characterize and monitor AR carried by bacteria from the entire food chain.

Keywords: plant-based products, ARG, PCR, antibiotic residues

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11 A Study on the Chemical Composition of Kolkheti's Sphagnum Peat Peloids to Evaluate the Perspective of Use in Medical Practice

Authors: Al. Tsertsvadze. L. Ebralidze, I. Matchutadze. D. Berashvili, A. Bakuridze

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Peatlands are landscape elements, they are formed over a very long period by physical, chemical, biologic, and geologic processes. In the moderate zone of Caucasus, the Kolkheti lowlands are distinguished by the diversity of relictual plants, a high degree of endemism, orographic, climate, landscape, and other characteristics of high levels of biodiversity. The unique properties of the Kolkheti region lead to the formation of special, so-called, endemic peat peloids. The composition and properties of peloids strongly depend on peat-forming plants. Peat is considered a unique complex of raw materials, which can be used in different fields of the industry: agriculture, metallurgy, energy, biotechnology, chemical industry, health care. They are formed in permanent wetland areas. As a result of decay, higher plants remain in the anaerobic area, with the participation of microorganisms. Peat mass absorbs soil and groundwater. Peloids are predominantly rich with humic substances, which are characterized by high biological activity. Humic acids stimulate enzymatic activity, regenerative processes, and have anti-inflammatory activity. Objects of the research were Kolkheti peat peloids (Ispani, Anaklia, Churia, Chirukhi, Peranga) possessing different formation phases. Due to specific physical and chemical properties of research objects, the aim of the research was to develop analytical methods in order to study the chemical composition of the objects. The research was held using modern instrumental methods of analysis: Ultraviolet-visible spectroscopy and Infrared spectroscopy, Scanning Electron Microscopy, Centrifuge, dry oven, Ultraturax, pH meter, fluorescence spectrometer, Gas chromatography-mass spectrometry (GC-MS/MS), Gas chromatography. Based on the research ration between organic and inorganic substances, the spectrum of micro and macro elements, also the content of minerals was determined. The content of organic nitrogen was determined using the Kjeldahl method. The total composition of amino acids was studied by a spectrophotometric method using standard solutions of glutamic and aspartic acids. Fatty acid was determined using GC (Gas chromatography). Based on the obtained results, we can conclude that the method is valid to identify fatty acids in the research objects. The content of organic substances in the research objects was held using GC-MS. Using modern instrumental methods of analysis, the chemical composition of research objects was studied. Each research object is predominantly reached with a broad spectrum of organic (fatty acids, amino acids, carbocyclic and heterocyclic compounds, organic acids and their esters, steroids) and inorganic (micro and macro elements, minerals) substances. Modified methods used in the presented research may be utilized for the evaluation of cosmetological balneological and pharmaceutical means prepared on the base of Kolkheti's Sphagnum Peat Peloids.

Keywords: modern analytical methods, natural resources, peat, chemistry

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10 Feasibility of Washing/Extraction Treatment for the Remediation of Deep-Sea Mining Trailings

Authors: Kyoungrean Kim

Abstract:

Importance of deep-sea mineral resources is dramatically increasing due to the depletion of land mineral resources corresponding to increasing human’s economic activities. Korea has acquired exclusive exploration licenses at four areas which are the Clarion-Clipperton Fracture Zone in the Pacific Ocean (2002), Tonga (2008), Fiji (2011) and Indian Ocean (2014). The preparation for commercial mining of Nautilus minerals (Canada) and Lockheed martin minerals (USA) is expected by 2020. The London Protocol 1996 (LP) under International Maritime Organization (IMO) and International Seabed Authority (ISA) will set environmental guidelines for deep-sea mining until 2020, to protect marine environment. In this research, the applicability of washing/extraction treatment for the remediation of deep-sea mining tailings was mainly evaluated in order to present preliminary data to develop practical remediation technology in near future. Polymetallic nodule samples were collected at the Clarion-Clipperton Fracture Zone in the Pacific Ocean, then stored at room temperature. Samples were pulverized by using jaw crusher and ball mill then, classified into 3 particle sizes (> 63 µm, 63-20 µm, < 20 µm) by using vibratory sieve shakers (Analysette 3 Pro, Fritsch, Germany) with 63 µm and 20 µm sieve. Only the particle size 63-20 µm was used as the samples for investigation considering the lower limit of ore dressing process which is tens to 100 µm. Rhamnolipid and sodium alginate as biosurfactant and aluminum sulfate which are mainly used as flocculant were used as environmentally friendly additives. Samples were adjusted to 2% liquid with deionized water then mixed with various concentrations of additives. The mixture was stirred with a magnetic bar during specific reaction times and then the liquid phase was separated by a centrifugal separator (Thermo Fisher Scientific, USA) under 4,000 rpm for 1 h. The separated liquid was filtered with a syringe and acrylic-based filter (0.45 µm). The extracted heavy metals in the filtered liquid were then determined using a UV-Vis spectrometer (DR-5000, Hach, USA) and a heat block (DBR 200, Hach, USA) followed by US EPA methods (8506, 8009, 10217 and 10220). Polymetallic nodule was mainly composed of manganese (27%), iron (8%), nickel (1.4%), cupper (1.3 %), cobalt (1.3%) and molybdenum (0.04%). Based on remediation standards of various countries, Nickel (Ni), Copper (Cu), Cadmium (Cd) and Zinc (Zn) were selected as primary target materials. Throughout this research, the use of rhamnolipid was shown to be an effective approach for removing heavy metals in samples originated from manganese nodules. Sodium alginate might also be one of the effective additives for the remediation of deep-sea mining tailings such as polymetallic nodules. Compare to the use of rhamnolipid and sodium alginate, aluminum sulfate was more effective additive at short reaction time within 4 h. Based on these results, sequencing particle separation, selective extraction/washing, advanced filtration of liquid phase, water treatment without dewatering and solidification/stabilization may be considered as candidate technologies for the remediation of deep-sea mining tailings.

Keywords: deep-sea mining tailings, heavy metals, remediation, extraction, additives

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9 Synchrotron Based Techniques for the Characterization of Chemical Vapour Deposition Overgrowth Diamond Layers on High Pressure, High Temperature Substrates

Authors: T. N. Tran Thi, J. Morse, C. Detlefs, P. K. Cook, C. Yıldırım, A. C. Jakobsen, T. Zhou, J. Hartwig, V. Zurbig, D. Caliste, B. Fernandez, D. Eon, O. Loto, M. L. Hicks, A. Pakpour-Tabrizi, J. Baruchel

Abstract:

The ability to grow boron-doped diamond epilayers of high crystalline quality is a prerequisite for the fabrication of diamond power electronic devices, in particular high voltage diodes and metal-oxide-semiconductor (MOS) transistors. Boron and intrinsic diamond layers are homoepitaxially overgrown by microwave assisted chemical vapour deposition (MWCVD) on single crystal high pressure, high temperature (HPHT) grown bulk diamond substrates. Various epilayer thicknesses were grown, with dopant concentrations ranging from 1021 atom/cm³ at nanometer thickness in the case of 'delta doping', up 1016 atom/cm³ and 50µm thickness or high electric field drift regions. The crystalline quality of these overgrown layers as regards defects, strain, distortion… is critical for the device performance through its relation to the final electrical properties (Hall mobility, breakdown voltage...). In addition to the optimization of the epilayer growth conditions in the MWCVD reactor, other important questions related to the crystalline quality of the overgrown layer(s) are: 1) what is the dependence on the bulk quality and surface preparation methods of the HPHT diamond substrate? 2) how do defects already present in the substrate crystal propagate into the overgrown layer; 3) what types of new defects are created during overgrowth, what are their growth mechanisms, and how can these defects be avoided? 4) how can we relate in a quantitative manner parameters related to the measured crystalline quality of the boron doped layer to the electronic properties of final processed devices? We describe synchrotron-based techniques developed to address these questions. These techniques allow the visualization of local defects and crystal distortion which complements the data obtained by other well-established analysis methods such as AFM, SIMS, Hall conductivity…. We have used Grazing Incidence X-ray Diffraction (GIXRD) at the ID01 beamline of the ESRF to study lattice parameters and damage (strain, tilt and mosaic spread) both in diamond substrate near surface layers and in thick (10–50 µm) overgrown boron doped diamond epi-layers. Micro- and nano-section topography have been carried out at both the BM05 and ID06-ESRF) beamlines using rocking curve imaging techniques to study defects which have propagated from the substrate into the overgrown layer(s) and their influence on final electronic device performance. These studies were performed using various commercially sourced HPHT grown diamond substrates, with the MWCVD overgrowth carried out at the Fraunhofer IAF-Germany. The synchrotron results are in good agreement with low-temperature (5°K) cathodoluminescence spectroscopy carried out on the grown samples using an Inspect F5O FESEM fitted with an IHR spectrometer.

Keywords: synchrotron X-ray diffaction, crystalline quality, defects, diamond overgrowth, rocking curve imaging

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8 The Association between Gene Polymorphisms of GPX, SEPP1, and SEP15, Plasma Selenium Levels, Urinary Total Arsenic Concentrations, and Prostate Cancer

Authors: Yu-Mei Hsueh, Wei-Jen Chen, Yung-Kai Huang, Cheng-Shiuan Tsai, Kuo-Cheng Yeh

Abstract:

Prostate cancer occurs in men over the age of 50, and rank sixth of the top ten cancers in Taiwan, and the incidence increased gradually over the past decade in Taiwan. Arsenic is confirmed as a carcinogen by International Agency for Research on (IARC). Arsenic induces oxidative stress may be a risk factor for prostate cancer, but the mechanism is not clear. Selenium is an important antioxidant element. Whether the association between plasma selenium levels and risk of prostate cancer are modified by different genotype of selenoprotein is still unknown. Glutathione peroxidase, selenoprotein P (SEPP1) and 15 kDa selenoprotein (SEP 15) are selenoprotein and regulates selenium transport and the oxidation and reduction reaction. However, the association between gene polymorphisms of selenoprotein and prostate cancer is not yet clear. The aim of this study is to determine the relationship between plasma selenium, polymorphism of selenoprotein, urinary total arsenic concentration and prostate cancer. This study is a hospital-based case-control study. Three hundred twenty-two cases of prostate cancer and age (±5 years) 1:1 matched 322 control group were recruited from National Taiwan University Hospital, Taipei Medical University Hospital, and Wan Fang Hospital. Well-trained personnel carried out standardized personal interviews based on a structured questionnaire. Information collected included demographic and socioeconomic characteristics, lifestyle and disease history. Blood and urine samples were also collected at the same time. The Research Ethics Committee of National Taiwan University Hospital, Taipei, Taiwan, approved the study. All patients provided informed consent forms before sample and data collection. Buffy coat was to extract DNA, and the polymerase chain reaction - restriction fragment length polymorphism (PCR-RFLP) was used to measure the genotypes of SEPP1 rs3797310, SEP15 rs5859, GPX1 rs1050450, GPX2 rs4902346, GPX3 rs4958872, and GPX4 rs2075710. Plasma concentrations of selenium were determined by inductively coupled plasma mass spectrometry (ICP-MS).Urinary arsenic species concentrations were measured by high-performance liquid chromatography links hydride generator and atomic absorption spectrometer (HPLC-HG-AAS). Subject with high education level compared to those with low educational level had a lower prostate cancer odds ratio (OR) Mainland Chinese and aboriginal people had a lower OR of prostate cancer compared to Fukien Taiwanese. After adjustment for age, educational level, subjects with GPX1 rs1050450 CT and TT genotype compared to the CC genotype have lower, OR of prostate cancer, the OR and 95% confidence interval (Cl) was 0.53 (0.31-0.90). SEPP1 rs3797310 CT+TT genotype compared to those with CC genotype had a marginally significantly lower OR of PC. The low levels of plasma selenium and the high urinary total arsenic concentrations had the high OR of prostate cancer in a significant dose-response manner, and SEPP1 rs3797310 genotype modified this joint association.

Keywords: prostate cancer, plasma selenium concentration, urinary total arsenic concentrations, glutathione peroxidase, selenoprotein P, selenoprotein 15, gene polymorphism

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7 Hyperspectral Imagery for Tree Speciation and Carbon Mass Estimates

Authors: Jennifer Buz, Alvin Spivey

Abstract:

The most common greenhouse gas emitted through human activities, carbon dioxide (CO2), is naturally consumed by plants during photosynthesis. This process is actively being monetized by companies wishing to offset their carbon dioxide emissions. For example, companies are now able to purchase protections for vegetated land due-to-be clear cut or purchase barren land for reforestation. Therefore, by actively preventing the destruction/decay of plant matter or by introducing more plant matter (reforestation), a company can theoretically offset some of their emissions. One of the biggest issues in the carbon credit market is validating and verifying carbon offsets. There is a need for a system that can accurately and frequently ensure that the areas sold for carbon credits have the vegetation mass (and therefore for carbon offset capability) they claim. Traditional techniques for measuring vegetation mass and determining health are costly and require many person-hours. Orbital Sidekick offers an alternative approach that accurately quantifies carbon mass and assesses vegetation health through satellite hyperspectral imagery, a technique which enables us to remotely identify material composition (including plant species) and condition (e.g., health and growth stage). How much carbon a plant is capable of storing ultimately is tied to many factors, including material density (primarily species-dependent), plant size, and health (trees that are actively decaying are not effectively storing carbon). All of these factors are capable of being observed through satellite hyperspectral imagery. This abstract focuses on speciation. To build a species classification model, we matched pixels in our remote sensing imagery to plants on the ground for which we know the species. To accomplish this, we collaborated with the researchers at the Teakettle Experimental Forest. Our remote sensing data comes from our airborne “Kato” sensor, which flew over the study area and acquired hyperspectral imagery (400-2500 nm, 472 bands) at ~0.5 m/pixel resolution. Coverage of the entire teakettle experimental forest required capturing dozens of individual hyperspectral images. In order to combine these images into a mosaic, we accounted for potential variations of atmospheric conditions throughout the data collection. To do this, we ran an open source atmospheric correction routine called ISOFIT1 (Imaging Spectrometer Optiman FITting), which converted all of our remote sensing data from radiance to reflectance. A database of reflectance spectra for each of the tree species within the study area was acquired using the Teakettle stem map and the geo-referenced hyperspectral images. We found that a wide variety of machine learning classifiers were able to identify the species within our images with high (>95%) accuracy. For the most robust quantification of carbon mass and the best assessment of the health of a vegetated area, speciation is critical. Through the use of high resolution hyperspectral data, ground-truth databases, and complex analytical techniques, we are able to determine the species present within a pixel to a high degree of accuracy. These species identifications will feed directly into our carbon mass model.

Keywords: hyperspectral, satellite, carbon, imagery, python, machine learning, speciation

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6 Raman Spectral Fingerprints of Healthy and Cancerous Human Colorectal Tissues

Authors: Maria Karnachoriti, Ellas Spyratou, Dimitrios Lykidis, Maria Lambropoulou, Yiannis S. Raptis, Ioannis Seimenis, Efstathios P. Efstathopoulos, Athanassios G. Kontos

Abstract:

Colorectal cancer is the third most common cancer diagnosed in Europe, according to the latest incidence data provided by the World Health Organization (WHO), and early diagnosis has proved to be the key in reducing cancer-related mortality. In cases where surgical interventions are required for cancer treatment, the accurate discrimination between healthy and cancerous tissues is critical for the postoperative care of the patient. The current study focuses on the ex vivo handling of surgically excised colorectal specimens and the acquisition of their spectral fingerprints using Raman spectroscopy. Acquired data were analyzed in an effort to discriminate, in microscopic scale, between healthy and malignant margins. Raman spectroscopy is a spectroscopic technique with high detection sensitivity and spatial resolution of few micrometers. The spectral fingerprint which is produced during laser-tissue interaction is unique and characterizes the biostructure and its inflammatory or cancer state. Numerous published studies have demonstrated the potential of the technique as a tool for the discrimination between healthy and malignant tissues/cells either ex vivo or in vivo. However, the handling of the excised human specimens and the Raman measurement conditions remain challenging, unavoidably affecting measurement reliability and repeatability, as well as the technique’s overall accuracy and sensitivity. Therefore, tissue handling has to be optimized and standardized to ensure preservation of cell integrity and hydration level. Various strategies have been implemented in the past, including the use of balanced salt solutions, small humidifiers or pump-reservoir-pipette systems. In the current study, human colorectal specimens of 10X5 mm were collected from 5 patients up to now who underwent open surgery for colorectal cancer. A novel, non-toxic zinc-based fixative (Z7) was used for tissue preservation. Z7 demonstrates excellent protein preservation and protection against tissue autolysis. Micro-Raman spectra were recorded with a Renishaw Invia spectrometer from successive random 2 micrometers spots upon excitation at 785 nm to decrease fluorescent background and secure avoidance of tissue photodegradation. A temperature-controlled approach was adopted to stabilize the tissue at 2 °C, thus minimizing dehydration effects and consequent focus drift during measurement. A broad spectral range, 500-3200 cm-1,was covered with five consecutive full scans that lasted for 20 minutes in total. The average spectra were used for least square fitting analysis of the Raman modes.Subtle Raman differences were observed between normal and cancerous colorectal tissues mainly in the intensities of the 1556 cm-1 and 1628 cm-1 Raman modes which correspond to v(C=C) vibrations in porphyrins, as well as in the range of 2800-3000 cm-1 due to CH2 stretching of lipids and CH3 stretching of proteins. Raman spectra evaluation was supported by histological findings from twin specimens. This study demonstrates that Raman spectroscopy may constitute a promising tool for real-time verification of clear margins in colorectal cancer open surgery.

Keywords: colorectal cancer, Raman spectroscopy, malignant margins, spectral fingerprints

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5 Date Palm Wastes Turning into Biochars for Phosphorus Recovery from Aqueous Solutions: Static and Dynamic Investigations

Authors: Salah Jellali, Nusiba Suliman, Yassine Charabi, Jamal Al-Sabahi, Ahmed Al Raeesi, Malik Al-Wardy, Mejdi Jeguirim

Abstract:

Huge amounts of agricultural biomasses are worldwide produced. At the same time, large quantities of phosphorus are annually discharged into water bodies with possible serious effects onto the environment quality. The main objective of this work is to turn a local Omani biomass (date palm fronds wastes: DPFW) into an effective material for phosphorus recovery from aqueous and the reuse of this P-loaded material in agriculture as ecofriendly amendment. For this aim, the raw DPFW were firstly impregnated with 1 M salt separated solutions of CaCl₂, MgCl₂, FeCl₃, AlCl₃, and a mixture of MgCl₂/AlCl₃ for 24 h, and then pyrolyzed under N2 flow at 500 °C for 2 hours by using an adapted tubular furnace (Carbolite, UK). The synthetized biochars were deeply characterized through specific analyses concerning their morphology, structure, texture, and surface chemistry. These analyses included the use of a scanning electron microscope (SEM) coupled with an energy-dispersive X-Ray spectrometer (EDS), X-Ray diffraction (XRD), Fourier Transform Infrared (FTIR), sorption micrometrics, and X-ray Fluorescence (XRF) apparatus. Then, their efficiency in recovering phosphorus was investigated in batch mode for various contact times (1 min to 3 h), aqueous pH values (from 3 to 11), initial phosphorus concentrations (10-100 mg/L), presence of anions (nitrates, sulfates, and chlorides). In a second step, dynamic assays, by using laboratory columns (height of 30 cm and diameter of 3 cm), were performed in order to investigate the recovery of phosphorus by the modified biochar with a mixture of Mg/Al. The effect of the initial P concentration (25-100 mg/L), the bed depth height (3 to 8 g), and the flow rate (10-30 mL/min) was assessed. Experimental results showed that the biochars physico-chemical properties were very dependent on the type of the used modifying salt. The main affected parameters concerned the specific surface area, microporosity area, and the surface chemistry (pH of zero-point charge and available functional groups). These characteristics have significantly affected the phosphorus recovery efficiency from aqueous solutions. Indeed, the P removal efficiency in batch mode varies from about 5 mg/g for the Fe-modified biochar to more than 13 mg/g for the biochar functionalized with Mg/Al layered double hydroxides. Moreover, the P recovery seems to be a time dependent process and significantly affected by the pH of the aqueous media and the presence of foreign anions due to competition phenomenon. The laboratory column study of phosphorus recovery by the biochar functionalized with Mg/Al layered double hydroxides showed that this process is affected by the used phosphorus concentration, the flow rate, and especially the column bed depth height. Indeed, the phosphorus recovered amount increased from about 4.9 to more than 9.3 mg/g used biochar mass of 3 and 8 g, respectively. This work proved that salt-modified palm fronds-derived biochars could be considered as attractive and promising materials for phosphorus recovery from aqueous solutions even under dynamic conditions. The valorization of these P-loaded-modified biochars as eco-friendly amendment for agricultural soils is necessary will promote sustainability and circular economy concepts in the management of both liquid and solid wastes.

Keywords: date palm wastes, Mg/Al double-layered hydroxides functionalized biochars, phosphorus, recovery, sustainability, circular economy

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4 Comparative Proteomic Profiling of Planktonic and Biofilms from Staphylococcus aureus Using Tandem Mass Tag-Based Mass Spectrometry

Authors: Arifur Rahman, Ardeshir Amirkhani, Honghua Hu, Mark Molloy, Karen Vickery

Abstract:

Introduction and Objectives: Staphylococcus aureus and coagulase-negative staphylococci comprises approximately 65% of infections associated with medical devices and are well known for their biofilm formatting ability. Biofilm-related infections are extremely difficult to eradicate owing to their high tolerance to antibiotics and host immune defences. Currently, there is no efficient method for early biofilm detection. A better understanding to enable detection of biofilm specific proteins in vitro and in vivo can be achieved by studying planktonic and different growth phases of biofilms using a proteome analysis approach. Our goal was to construct a reference map of planktonic and biofilm associated proteins of S. aureus. Methods: S. aureus reference strain (ATCC 25923) was used to grow 24 hours planktonic, 3-day wet biofilm (3DWB), and 12-day wet biofilm (12DWB). Bacteria were grown in tryptic soy broth (TSB) liquid medium. Planktonic growth was used late logarithmic bacteria, and the Centres for Disease Control (CDC) biofilm reactor was used to grow 3 days, and 12-day hydrated biofilms, respectively. Samples were subjected to reduction, alkylation and digestion steps prior to Multiplex labelling using Tandem Mass Tag (TMT) 10-plex reagent (Thermo Fisher Scientific). The labelled samples were pooled and fractionated by high pH RP-HPLC which followed by loading of the fractions on a nanoflow UPLC system (Eksigent UPLC system, AB SCIEX). Mass spectrometry (MS) data were collected on an Orbitrap Elite (Thermo Fisher Scientific) Mass Spectrometer. Protein identification and relative quantitation of protein levels were performed using Proteome Discoverer (version 1.3, Thermo Fisher Scientific). After the extraction of protein ratios with Proteome Discoverer, additional processing, and statistical analysis was done using the TMTPrePro R package. Results and Discussion: The present study showed that a considerable proteomic difference exists among planktonic and biofilms from S. aureus. We identified 1636 total extracellular secreted proteins, of which 350 and 137 proteins of 3DWB and 12DWB showed significant abundance variation from planktonic preparation, respectively. Of these, simultaneous up-regulation in between 3DWB and 12DWB proteins such as extracellular matrix-binding protein ebh, enolase, transketolase, triosephosphate isomerase, chaperonin, peptidase, pyruvate kinase, hydrolase, aminotransferase, ribosomal protein, acetyl-CoA acetyltransferase, DNA gyrase subunit A, glycine glycyltransferase and others we found in this biofilm producer. On the contrary, simultaneous down-regulation in between 3DWB and 12DWB proteins such as alpha and delta-hemolysin, lipoteichoic acid synthase, enterotoxin I, serine protease, lipase, clumping factor B, regulatory protein Spx, phosphoglucomutase, and others also we found in this biofilm producer. In addition, we also identified a big percentage of hypothetical proteins including unique proteins. Therefore, a comprehensive knowledge of planktonic and biofilm associated proteins identified by S. aureus will provide a basis for future studies on the development of vaccines and diagnostic biomarkers. Conclusions: In this study, we constructed an initial reference map of planktonic and various growth phase of biofilm associated proteins which might be helpful to diagnose biofilm associated infections.

Keywords: bacterial biofilms, CDC bioreactor, S. aureus, mass spectrometry, TMT

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3 Infrared Spectroscopy Fingerprinting of Herbal Products- Application of the Hypericum perforatum L. Supplements

Authors: Elena Iacob, Marie-Louise Ionescu, Elena Ionescu, Carmen Elena Tebrencu, Oana Teodora Ciuperca

Abstract:

Infrared spectroscopy (FT-IR) is an advanced technique frequently used to authenticate both raw materials and final products using their specific fingerprints and to determine plant extracts biomarkers based on their functional groups. In recent years the market for Hypericum has grown rapidly and also has grown the cases of adultery/replacement, especially for Hypericum perforatum L.specie. Presence/absence of same biomarkers provides preliminary identification of Hypericum species in safe use in the manufacture of food supplements. The main objective of the work was to characterize the main biomarkers of Hypericum perforatum L. (St. John's wort) and identify this species in herbal food supplements after specific FT-IR fingerprint. An experimental program has been designed in order to test: (1) raw material (St. John's wort); (2)intermediate raw materials (St. John's wort dry extract ); (3) the finished products: tablets based on powders, on extracts, on powder and extract, hydroalcoholic solution from herbal mixture based on St. John's wort. The analyze using FTIR infrared spectroscopy were obtained raw materials, intermediates and finished products spectra, respectively absorption bands corresponding and similar with aliphatic and aromatic structures; examination was done individually and through comparison between Hypericum perforatum L. plant species and finished product The tests were done in correlation with phytochemical markers for authenticating the specie Hypericum perforatum L.: hyperoside, rutin, quercetin, isoquercetin, luteolin, apigenin, hypericin, hyperforin, chlorogenic acid. Samples were analyzed using a Shimatzu FTIR spectrometer and the infrared spectrum of each sample was recorded in the MIR region, from 4000 to 1000 cm-1 and then the fingerprint region was selected for data analysis. The following functional groups were identified -stretching vibrations suggests existing groups in the compounds of interest (flavones–rutin, hyperoside, polyphenolcarboxilic acids - chlorogenic acid, naphtodianthrones- hypericin): oxidril groups (OH) free alcohol type: rutin, hyperoside, chlorogenic acid; C = O bond from structures with free carbonyl groups of aldehyde, ketone, carboxylic, ester: hypericin; C = O structure with the free carbonyl of the aldehyde groups, ketone, carboxylic acid, esteric/C = O free bonds present in chlorogenic acid; C = C bonds of the aromatic ring (condensed aromatic hydrocarbons, heterocyclic compounds) present in all compounds of interest; OH phenolic groups: present in all compounds of interest, C-O-C groups from glycoside structures: rutin, hyperoside, chlorogenic acid. The experimental results show that: (I)The six fingerprint region analysis indicated the presence of specific functional groups: (1) 1000 - 1130 cm-1 (C-O–C of glycoside structures); (2) 1200-1380 cm-1 (carbonyl C-O or O-H phenolic); (3) 1400-1450 cm-1 (C=C aromatic); (4) 1600- 1730 cm-1 (C=O carbonyl); (5) 2850 - 2930 cm-1 (–CH3, -CH2-, =CH-); (6) 338-3920 cm-1 (OH free alcohol type); (II)Comparative FT-IR spectral analysis indicate the authenticity of the finished products ( tablets) in terms of Hypericum perforatum L. content; (III)The infrared spectroscopy is an adequate technique for identification and authentication of the medicinal herbs , intermediate raw material and in the food supplements less in the form of solutions where the results are not conclusive.

Keywords: Authentication, FT-IR fingerprint, Herbal supplements, Hypericum perforatum L.

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2 Reflection of Landscape Agrogenization in the Soil Cover Structure and Profile Morphology: Example of Lithuania Agroecosystem

Authors: Jonas Volungevicius, Kristina Amaleviciute, Rimantas Vaisvalavicius, Alvyra Slepetiene, Darijus Veteikis

Abstract:

Lithuanian territory is characterized by landscape with prevailing morain hills and clayey lowlands. The largest part of it has endured agrogenization of various degrees which was the cause of changes both in the structure of landscape and soil cover, transformations of soil profile and degradation of natural background soils. These changes influence negatively geoecological potential of landscape and soil and contribute to the weakening of the sustainability of agroecosystems. Research objective: to reveal the landscape agrogenization induced alterations of catenae and their appendant soil profiles in Lithuanian morain hills and clayey lowlands. Methods: Soil cover analysis and catenae charting was conducted using landscape profiling; soil morphology detected and soil type identified following WRB 2014. Granulometric composition of soil profiles was obtained by laser diffraction method (lazer diffractometer Mastersizer 2000). pH was measured in H2O extraction using potentiometric titration; SOC was determined by the Tyurin method modified by Nikitin, measuring with spectrometer Cary 50 (VARIAN) in 590 nm wavelength using glucose standards. Results: analysis showed that the decrease of forest vegetation and the other natural landscape components following the agrogenization of the research area influenced differently but significantly the structural alterations in soil cover and vertical soil profile. The research detected that due to landscape agrogenization, the suppression of zone-specific processes and the intensification of inter-zone processes determined by agrogenic factors take place in Lithuanian agroecosystems. In forested hills historically prevailing Retisols and Histosols territorial complex is transforming into the territorial complex of Regosols, Deluvial soils and drained Histosols. Processes taking place are simplification of vertical profile structure, intensive rejuvenation of profile, disappearance of the features of zone-specific soil-forming processes (podzolization, lessivage, gley formation). Erosion and deluvial processes manifest more intensively and weakly accumulating organic material more intensively spread in a vertical soil profile. The territorial soil complex of Gleyic Luvisols and Gleysols dominating in forested clayey lowlands subjected to agrogenization is transformed into the catena of drained Luvisols and pseudo Cambisols. The best expressed are their changes in moisture regime (morphological features of gley and stagnic properties are on decline) together with alterations of pH and distribution and intensity of accumulation of organic matter in profile. A specific horizon, antraquic, uncharacteristic to natural soil formation is appearing. Important to note that due to deep ploughing and other agrotechnical measures, the natural vertical differentiation of clay particles in a soil profile is destroyed which leads not only to alterations of physical qualities of soil, but also encumbers the identification of Luvisols by creating presumptions to misidentify them as Cambisols. The latter have never developed in these ecosystems under the present climatic conditions. Acknowledgements: This work was supported by the National Science Program: The effect of long-term, different-intensity management of resources on the soils of different genesis and on other components of the agro-ecosystems [grant number SIT-9/2015] funded by the Research Council of Lithuania.

Keywords: agroecosystems, landscape agrogenization, luvisols, retisols, transformation of soil profile

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1 Sampling and Chemical Characterization of Particulate Matter in a Platinum Mine

Authors: Juergen Orasche, Vesta Kohlmeier, George C. Dragan, Gert Jakobi, Patricia Forbes, Ralf Zimmermann

Abstract:

Underground mining poses a difficult environment for both man and machines. At more than 1000 meters underneath the surface of the earth, ores and other mineral resources are still gained by conventional and motorised mining. Adding to the hazards caused by blasting and stone-chipping, the working conditions are best described by the high temperatures of 35-40°C and high humidity, at low air exchange rates. Separate ventilation shafts lead fresh air into a mine and others lead expended air back to the surface. This is essential for humans and machines working deep underground. Nevertheless, mines are widely ramified. Thus the air flow rate at the far end of a tunnel is sensed to be close to zero. In recent years, conventional mining was supplemented by mining with heavy diesel machines. These very flat machines called Load Haul Dump (LHD) vehicles accelerate and ease work in areas favourable for heavy machines. On the other hand, they emit non-filtered diesel exhaust, which constitutes an occupational hazard for the miners. Combined with a low air exchange, high humidity and inorganic dust from the mining it leads to 'black smog' underneath the earth. This work focuses on the air quality in mines employing LHDs. Therefore we performed personal sampling (samplers worn by miners during their work), stationary sampling and aethalometer (Microaeth MA200, Aethlabs) measurements in a platinum mine in around 1000 meters under the earth’s surface. We compared areas of high diesel exhaust emission with areas of conventional mining where no diesel machines were operated. For a better assessment of health risks caused by air pollution we applied a separated gas-/particle-sampling tool (or system), with first denuder section collecting intermediate VOCs. These multi-channel silicone rubber denuders are able to trap IVOCs while allowing particles ranged from 10 nm to 1 µm in diameter to be transmitted with an efficiency of nearly 100%. The second section is represented by a quartz fibre filter collecting particles and adsorbed semi-volatile organic compounds (SVOC). The third part is a graphitized carbon black adsorber – collecting the SVOCs that evaporate from the filter. The compounds collected on these three sections were analyzed in our labs with different thermal desorption techniques coupled with gas chromatography and mass spectrometry (GC-MS). VOCs and IVOCs were measured with a Shimadzu Thermal Desorption Unit (TD20, Shimadzu, Japan) coupled to a GCMS-System QP 2010 Ultra with a quadrupole mass spectrometer (Shimadzu). The GC was equipped with a 30m, BP-20 wax column (0.25mm ID, 0.25µm film) from SGE (Australia). Filters were analyzed with In-situ derivatization thermal desorption gas chromatography time-of-flight-mass spectrometry (IDTD-GC-TOF-MS). The IDTD unit is a modified GL sciences Optic 3 system (GL Sciences, Netherlands). The results showed black carbon concentrations measured with the portable aethalometers up to several mg per m³. The organic chemistry was dominated by very high concentrations of alkanes. Typical diesel engine exhaust markers like alkylated polycyclic aromatic hydrocarbons were detected as well as typical lubrication oil markers like hopanes.

Keywords: diesel emission, personal sampling, aethalometer, mining

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