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The change in the corrosion activities of SS304 and the carbon steel A36 were studied during their exposure for 30 days to hybrid pumice-Portland cement extract (CE), to simulate the concrete-pore environment. The ionic composition and the initial pH (12.99) of the CE were influenced by the reduction of Portland cement (PC) content, volcanic pumice oxides and alkaline activators. Because of the air CO2 dissolution, the pH decreased and maintained a constant value ≈ 9.10 (established dynamic ionic equilibrium). The CE promoted the passivation of both steels and their free corrosion potential (OCP) reached positive values. On the surfaces, Fe and Cr oxides were formed, according to the nature of the steel. Over the time of exposure, the presence of chloride ions in the pumice caused a localized pitting attack, and for carbon steel, this fact may indicate an intermediate risk of corrosion. The chloride effect was retarded by the accumulation of SO42- ions at the steel surfaces. Based on electrochemical impedance (EIS), the polarization resistance (Rp) and the thickness of the passive layers were calculated. Their values were compared with those previously reported for the steels exposed to CEs of Portland and supersulfated cements, and the hybrid cement was considered as a PC "green" alternative.

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Corrosion processes at cut edges of galvanized steels proceed as highly localized electrochemical reactions between the exposed bulk steel matrix and the protective thin metallic coating of a more electrochemically active material. Scanning microelectrochemical techniques can thus provide the spatially resolved information needed to assess the corrosion initiation and propagation phenomena, yet most methods scan cut edge sections as embedded in insulating resin to achieve a flat surface for scanning purposes. In this work, the galvanized coatings on both sides of the material were concomitantly exposed to simulated acid rain while characterizing the cut edge response using SECM and SVET techniques, thereby maintaining the coupled effects through the exposure of the whole system as rather realistic operation conditions. The cut edges were shown to strongly promote oxygen consumption and subsequent alkalization to pH 10-11 over the iron, while diffusion phenomena eventually yielded the complete depletion of oxygen and pH neutralization of the nearby electrolyte. In addition, the cathodic activation of the exposed iron was intensified with a thinner coating despite the lower presence of sacrificial anode, and preferential sites of the attack in the corners revealed highly localized acidification below pH 4, which sustained hydrogen evolution at spots of the steel-coating interface.

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Stainless steel SS430 and carbon steel B450C were exposed for 30 days to the aqueous extract of sodium silicate-modified limestone-Portland cement as an alternative for the partial replacement of the Portland cement clinker. The initial pH of 12.60 was lowered and maintained at an average of 9.60, associated with air CO2 dissolution and acidification. As a result, the carbon steel lost its passive state, and the corrosion potential (OCP) reached a negative value of up to 296 mV, forming the corrosion layer of FeO, and FeOOH. In the meaning time, on the stainless steel SS430 surface, a passive layer of Cr2O3 grew in the presence of FeO, Fe2O3 and Cr(OH)3 corrosion products; thus, the OCP shifted to more positive values of +150 mV. It is suggested that a self-repassivation process took place on the SS430 surface due to the accumulation of alkaline sulfates on the interface. Because of the chloride attack, SS430 presented isolated pits, while on B450C, their area was extended. The quantitative analysis of EIS Nyquist and Bode diagrams revealed that the Rp of the corrosion process for SS430 was 2500 kΩcm2, ≈32 times lower in magnitude than on B450C, for which the passive layer tended to disappear, while that on SS430 was ≈0.82 nm.

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This study provides a microanalytical characterization of pigment fragments from the painting "Allegory to the Arts" and two portraits, "Rubens" and "Tintoretto," by Léon Pallière. The fragments were surface-analyzed using several near-surface methods to acquire information on the materials and determine the painting techniques utilized before the restoration. Scanning electron microscopy/energy-dispersive X-ray spectrometry (SEM/EDS), Raman spectroscopy coupled to an optical microscope (Raman microprobe), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) revealed organic materials, hydrocerussite (Pb3(CO3)2(OH)2), cerussite (PbCO3), zincite (ZnO), chalcopyrite (CuFeS2), nepheline (K(Na,K)3AlSi4O16), calcite (CaCO3), brookite (TiO2), kinoshitalite (Ba3(Si2Al2)O10(OH)2), hematite (Fe2O3), barium magnesium silicate (Ba2Mg(Si2O7)), and aluminosilicates. Also identified were vermilion/cinnabar (HgS), copper phthalocyanine blue (C32H16CuN8), and mendipite (Pb3Cl2O2), in addition to the use of gold leaf in one of the artworks. SEM/EDS provided information on the chemical composition and surface morphology of the fragments, and XRD revealed crystalline raw materials (minerals or their synthetic analogs) used in the paintings. Raman microprobe was particularly useful in identifying pigments, providing a uniquely specific and sensitive means of identifying inorganic and organic compounds.

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Carbon steel B450C and low-chromium stainless steel SS430 were exposed for 30 days to supersulfated "SS1" cement extract solution, considered as a "green" alternative for partial replacement of the Portland cement clinker. The initial pH of 12.38 dropped since the first day to 7.84, accompanied by a displacement to more negative values of the free corrosion potential (OCP) of the carbon steel up to ≈-480.74 mV, giving the formation of γ-FeOOH, α-FeOOH and Fe2O3, as suggested by XRD and XPS analysis. In the meantime, the OCP of the SS430 tended towards more positive values (+182.50 mV), although at lower pH, and XPS analysis revealed the presence of Cr(OH)3 and FeO as corrosion products, as well the crystals of CaCO3, NaCl and KCl. On both surfaces, a localized corrosion attack was observed in the vicinity of local cathodes (Cu, Mn-carbides, Cr-nitrides, among others), influenced by the presence of Cl- ions in the "SS1" extract solution, originating from the pumice. Two equivalent circuits were proposed for the quantitative analysis of EIS Nyquist and Bode diagrams, whose data were correlated with the OCP values and pH change in time of the "SS1" extract solution. The thickness of the corrosion layer formed on the SS430 surface was ≈0.8 nm, while that on the B450C layer was ≈0.3 nm.

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Between June 2018 and April 2019, a sampling campaign was carried out to collect PM2.5, monitoring meteorological parameters and anthropogenic events in the Sartenejas Valley, Venezuela. We develop a logistic model for PM2.5 exceedances (≥ 12.5 µg m-3). Source appointment was done using elemental composition and morphology of PM by scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS). A proposal of an early warning system (EWS) for PM pollution episodes is presented. The logistic model has a holistic success rate of 94%, with forest fires and motor vehicle flows as significant variables. Source appointment analysis by occurrence of events showed that samples with higher concentrations of PM had carbon-rich particles and traces of K associated with biomass burning, as well as aluminosilicates and metallic elements associated with resuspension of soil dust by motor-vehicles. Quantitative source appointment analysis showed that soil dust, garbage burning/marine aerosols and wildfires are three majority sources of PM. An EWS for PM pollution episodes around the Sartenejas Valley is proposed considering the variables and elements mentioned.

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Croton lechleri, commonly known as Dragon's blood, is a tree cultivated in the northwest Amazon rainforest of Ecuador and Peru. This tree produces a deep red latex which is composed of different natural products such as phenolic compounds, alkaloids, and others. The chemical structures of these natural products found in C. lechleri latex are promising corrosion inhibitors of admiralty brass (AB), due to the number of heteroatoms and π structures. In this work, three different extracts of C. lechleri latex were obtained, characterized phytochemically, and employed as novel green corrosion inhibitors of AB. The corrosion inhibition efficiency (IE%) was determined in an aqueous 0.5 M HCl solution by potentiodynamic polarization (Tafel plots) and electrochemical impedance spectroscopy, measuring current density and charge transfer resistance, respectively. In addition, surface characterization of AB was performed by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy techniques. Chloroform alkaloid-rich extracts resulted in IE% of 57% at 50 ppm, attributed to the formation of a layer of organic compounds on the AB surface that hindered the dezincification process. The formulation of corrosion inhibitors from C. lechleri latex allows for the valorization of non-edible natural sources and the diversification of the offer of green corrosion inhibitors for the chemical treatment of heat exchangers.

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The production of electronic waste due to technological development, economic growth and increasing population has been rising fast, pushing for solutions before the environmental pressure achieves unprecedented levels. Recently, it was observed that many extractive metallurgy alternatives had been considered to recover value from this type of waste. Regarding pyrometallurgy, little is known about the low-temperature processing applied before fragmentation and subsequent component separation. Therefore, the present manuscript studies such alternative based on scanning electron microscopy characterization. The sample used in the study was supplied by a local recycling center in Rio de Janeiro, Brazil. The mass loss was constant at around 30% for temperatures higher than 300 °C. Based on this fact, the waste material was then submitted to low-temperature processing at 350 °C followed by attrition disassembling, size classification, and magnetic concentration steps. In the end, this first report of the project shows that 15% of the sample was recovered with metallic components with high economic value, such as Cu, Ni, and Au, indicating that such methods could be an interesting alternative to be explored in the future for the development of alternative electronic waste extraction routes.

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The study evaluated the spatial and seasonal variations of microplastic abundances in water, sediments, and commercial fishes of a semi-urban tourist impacted estuary in the Gulf of Mexico, Mexico. The prevalence of microplastics (MPs) elucidated diffuse sources namely long-range transport, domestic, agricultural, fishing, industrial and recreational activities and the local climatic conditions. Seasonally, the mean abundances of MPs in both water and sediments were high during Nortes (strong winds) followed by the dry and rainy seasons. Overall, black and blue colored MPs dominated the region and all the recovered plastics were fibers. The commercial fishes (n = 187) contained 881 MPs in their gastrointestinal tracts, suggesting that the food web of the estuary is highly prone to microplastic contamination. SEM images of extracted plastic fibers presented surface morphologies that are impacted by physical strains. Further, the elemental characterization of fibers using EDX displayed significant peaks of Al, As, Cl, Cr, Cu, Pb, and Zn that were used as additives during the production of plastics. The main types of polymers included low-density polyethylene, polyester, polypropylene, polycarbonate, rayon, polyvinyl chloride, polyacrylonitrile, polyamide, nylon and polyethylene terephthalate. MP abundances demonstrated in this study elucidate that estuaries are a major conduit for land-derived plastics to the ocean and the results will aid in implementing remedial/clean up actions of the estuary for better conservation of the ecosystem.

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Annually, millions of tons of foods are generated with the purpose to feed the growing world population. One particular eatable is orange, the production of which in 2018 was 75.54 Mt. One way to valorize the orange residue is to produce bioethanol by fermenting the reducing sugars generated from orange peel. Hence, the objective of the present work was to determine the experimental conditions to obtain the maximum yield of reducing sugars from orange peel using a diluted acid hydrolysis process. A proximate and chemical analysis of the orange peel were conducted. For the hydrolysis, two factorial designs were prepared to measure the glucose and fructose concentration with the 3,5-DNS acid method and UV-Visible spectroscopy. The factors were acid concentration, temperature and hydrolysis time. After the hydrolysis, the orange peel samples were subjected to an elemental SEM-EDS analysis. The results for the orange peel were 73.530% of moisture, 99.261% of volatiles, 0.052% of ash, 0.687% of fixed carbon, 19.801% of lignin, 69.096% of cellulose and 9.015% of hemicellulose. The highest concentration of glucose and fructose were 24.585 and 9.709 g/L, respectively. The results highlight that sugar production is increased by decreasing the acid concentration.

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To access the sources of air pollutants is crucial to control atmospheric pollution in urban areas, minimizing human exposure. Particulate matter is a pollutant of great concern making its chemical and morpho-structural characterization of enormous importance. The present work aims at the characterization of atmospheric PM10 and PM2.5. Data of the aerosol mass concentration was correlated by multivariate analysis with water-soluble ion fraction composition accessed by ion chromatography (IC), as well as with meteorological information and air mass backward trajectories. The gravimetric analysis presented average values 3 to 4 times higher than the guide values recommended by the World Health Organization (WHO). A morpho-structural analysis by SEM/FEG coupled to EDS was also carried out identifying the coarse fraction elements from minerals and from soil resuspension organic spherical particles that originated from combustion processes as well as Ti, associated with long-distance transportation. In the fine fraction, Zn with origin probably in tires and vehicle brakes was found. These origins were confirmed by the air masses' backward trajectories obtained by the HYSPLIT model (NOAA). This study contributes to a better understanding of the complex composition of the particulate material in the atmosphere of Araraquara City, resulting from the combination of local and long-distance sources, and serves as a basis for the comparison with future studies related to the air quality at this and other regions in Brazil and in the world.

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This study evaluated in the dry and rainy periods, the anthropogenic influence and the hydrodynamics in the distribution of plastic items in surface waters and bottom and beach sediments of the Jurujuba (Guanabara Bay, low and medium hydrodynamic) and Itaipu (oceanic region, high hydrodynamics) embayments; places of cultivation and extraction of mussels. Microplastics were 83% of the wastes collected, with a higher average concentration (138.41 items.kg-1) in beach sediments. High density polyethylene (HDPE) (38%), polypropylene (21%), and styrene (10%) were the most frequent polymers. There was no difference between the water and bottom sediment samples in the different embayments, in the studied periods, different from that observed in the beach sediment samples, with higher concentrations in the rainy season in Jurujuba. The results suggest that beach sediments are the best compartment to understand the dynamics of the distribution of plastic waste over time.

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Plastic pollution in the oceans has become a global problem, but its documentation is disparate around the world. We assess the abundance and type of microplastics in three benthic matrices: mussels, small fishes, and bottom water; in three sites nearby Puerto Madryn city (Patagonia, Argentina). Microplastics were present in the three matrices for all sites sampled. The average amounts of items observed were 1.6 and 0.3 per total wet weight in fishes and mussels, respectively, and 10.5 per liter in bottom water. Mussels and fishes presented a difference of microplastics size comparing with the surrounding bottoms waters; fishes also presented color discrimination, suggesting the necessity of more than one bioindicator to perform microplastic pollution monitoring. Moreover, small fishes had more MPs in their gastrointestinal tracts than bigger ones. The present study is the first one about the interaction between MPs and small aquatic organisms in coastal marine environments from Patagonia.

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Air pollution causes deleterious effects on human health with aerosols being among the most polluting agents. The objective of this work is the characterization of the PM2.5 and PM10 aerosol mass in the atmosphere. The methods of analysis include WD-XRF and EDS. Data were correlated with meteorological information and air mass trajectories (model HYSPLIT) by multivariate analysis. A morphological structural analysis was also carried out to identify the probable sources of atmospheric aerosols in the city of São José do Rio Preto, Brazil. The mean mass concentration values obtained were 24.54 µg/m3 for PM10, above the WHO annual standard value of 20 µg/m3 and 10.88 µg/m3 for PM2.5 whose WHO recommended limit is 10 µg/m3. WD-XRF analysis of the samples revealed Si and Al as major components of the coarse fraction. In the fine fraction, the major elements were Al and S. The SEM-FEG characterization allowed identifying the morphology of the particles in agglomerates, ellipsoids and filaments in the PM10, besides spherical in the PM2.5. The analysis by EDS corroborated WD-XRF results, identifying the crustal elements, aluminosilicates and elements of anthropogenic origin in the coarse fraction. For the fine fraction crustal elements were also identified; aluminosilicates, black carbon and spherical particles (C and O) originating from combustion processes were predominant. The use of multivariate analysis to correlate air mass trajectories with the results of the morpho-structural characterization of the particulate matter allowed confirmation of the complex composition of the particles resulting from the combination of both local and long-distance sources.

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BACKGROUND: The use of scanning electron microscopy (SEM) and energy-dispersive spectrometry (EDS) was investigated to understand the wear mechanisms from a metal-on-polyethylene bearing couple. Morphological features of femoral head acetabular liner, and isolated particles resulting from hip wear testing were evaluated. EDS was proposed to investigate the polymeric nature of the particles isolated from the wear testing. METHODS: In this work, 28-mm conventional ultra-high-molecular-weight polyethylene acetabular liners paired with metallic heads were tested in a hip wear simulator over 2 million cycles. SEM-EDS was employed to investigate wear mechanisms on hip implant components and associated wear debris. RESULTS: SEM showed worn surfaces for both hip components, and a significant volume of ultra-high-molecular-weight polyethylene wear particles resulting from hip wear testing. Particles were classified into 3 groups, which were then correlated to wear mechanisms. Group I had particles with smooth surfaces, group II consisted of particles with rough surfaces, and group III comprised aggregate-like particles. Group I EDS revealed that particles from groups I and II had a high C/O ratio raising a concern about the particle source. On the other hand, particles from group III had a low C/O ratio, supporting the hypothesis that they resulted from the wear of acetabular liner. Most of particles identified in group III were in the biologically active size range (0.3 to 20 µm). CONCLUSION: The use of optical and electron microscopy enabled the morphological characterization of worn surfaces and wear debris, while EDS was essential to elucidate the chemical composition of isolated debris.

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Abstract This study evaluated the effect of air-abrasion on t®m phase transformation, roughness, topography and the elemental composition of three Y-TZP (Yttria-stabilized tetragonal zirconia polycrystal) dental ceramics: two conventional (Lava Frame and IPS ZirCad) and one with high-translucency (Lava Plus). Plates obtained from sintered blocks of each ceramic were divided into four groups: AS (as-sintered); 30 (air-abrasion with 30 mm Si-coated Al2O3 particles); 50 (air-abrasion with 50 mm Al2O3 particles) and 150 (air-abrasion with 150 mm Al2O3 particles). After the treatments, the plates were submitted to X-ray diffractometry; 3-D profilometry and SEM/EDS. The AS surfaces were composed of Zr and t phases. All treatments produced t®m phase transformation in the ceramics. The diameter of air-abrasion particles influenced the roughness (150>50>30>AS) and the topography. SEM analysis showed that the three treatments produced groove-shaped microretentions on the ceramic surfaces, which increased with the diameter of air-abrasion particles. EDS showed a decrease in Zr content along with the emergence of O and Al elements after air-abrasion. Presence of Si was also detected on the plates air-abraded with 30 mm Si-coated Al2O3 particles. It was concluded that irrespective of the type and diameter of the particles, air-abrasion produced t®m phase transformation, increased the roughness and changed the elemental composition of the three Y-TZP dental ceramics. Lava Plus also behaved similarly to the conventional Y-TZP ceramics, indicating that this high translucency ceramic could be more suitable to build monolithic ceramic restorations in the aesthetic restorative dentistry field.

Resumo Este estudo avaliou o efeito da abrasão a ar na transformação de fase t®m, na rugosidade, topografia e composição elementar de três cerâmicas Y-TZP (Zircônia tetragonal policristalina estabilizada por ítrio): duas convencionais (Lava Frame e ZirCad) e uma de alta translucidez (Lava Plus). Placas obtidas de blocos sinterizados de cada cerâmica foram divididos em quatro grupos: AS (pré-sinterizado); 30 (jateamento com partículas de Al2O3 de 30 mm cobertas com Si); 50 (jateamento com partículas de Al2O3 de 50 mm) e 150 (jateamento com partículas de Al2O3 de 150 mm). Após os tratamentos, as placas foram submetidas à difratometria de Rx, perfilometria 3-D e microscopia eletrônica de varredura com espectroscopia de energia dispersiva de Rx (SEM/EDS). As superfícies pré-sinterizadas apresentaram predominantemente Zr e fase tetragonal. Todos os tratamentos superficiais produziram transformação t®m nas cerâmicas avaliadas. A topografia e a rugosidade foram influenciadas pelo diâmetro das partículas abrasivas (150>50>30>AS). A análise através de SEM mostrou que os três tratamentos produziram fendas retentivas nas superfícies das cerâmicas, por influência do tamanho das partículas. A análise através de EDS mostrou uma diminuição da concentração de Zr, paralela ao surgimento de O e Al, após o jateamento. No grupo tratado com partículas de Al2O3 de 30 mm cobertas com Si foi também observado um aumento de Si após o jateamento. Concluiu-se que, independente do tipo e do diâmetro das partículas, o jateamento produziu transformação t®m, aumentou a rugosidade e alterou a composição elementar das cerâmicas avaliadas. A Lava Plus apresentou comportamento semelhante às cerâmicas convencionais, indicando que esta cerâmica de alta translucidez pode ser mais adequada à confecção de restaurações monolíticas no campo da odontologia estética restauradora.

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One of the biggest environmental problems existing today is air pollution, which is characterized by the presence of toxic gases and metal pollutants, the latter of which is generally associated with emissions of particulate matter (PM) from industries or automotive vehicles. Biomonitoring is a method that can be used to assess air pollution levels because it makes it possible to determine what effects these air pollutants cause in living organisms and their responses. The species Lolium multiflorum Lam., known as ryegrass, is considered a good bioindicator of metals, since it accumulates these substances during exposure. This study proposes to conduct an integrated assessment of air quality using two different monitoring methodologies: biomonitoring with L. multiflorum and active monitoring in areas with different levels of urbanization and industrialization. Concentrations found in ryegrass plants revealed high levels of Pb, Cr, Zn, and Cu, indicating that vehicular and industrial emissions were the main sources of pollution. Analysis of PM also revealed soot and biogenic particles, which can transport metals. Therefore, with the proposed method, the anthropogenic impact on air pollution in the investigated area could be clearly demonstrated.

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Understanding the geochemistry of basalt alteration is central to the study of agriculture systems. Various nano-minerals play an important role in the mobilization of contaminants and their subsequent uptake by plants. We present a new analytical experimental approach in combination with an integrated analytical protocol designed to study basalt alteration processes. Recently, throughout the world, ultra-fine and nano-particles derived from basalt dust wastes (BDW) during "stonemeal" soil fertilizer application have been of great concern for their possible adverse effects on human health and environmental pollution. Samples of BDW utilized were obtained from companies in the Nova Prata mining district in southern Brazil for chemical characterization and nano-mineralogy investigation, using an integrated application of advanced characterization techniques such as X-ray diffraction (XRD), High Resolution-Transmission Electron microscopy (HR-TEM)/Energy Dispersive Spectroscopy (EDS)/(selected-area diffraction pattern) SAED, Field Emission-Scanning Electron Microscopy (FE-SEM/EDS), and granulometric distribution analysis. The investigation has revealed that BDW materials are dominated by SiO2, Al2O3, and Fe2O3, with a complex micromineralogy including alkali feldspar, augite, barite, labradorite, hematite, heulandrite, gypsum, kaolinite, quartz, and smectite. In addition, we have identified a number of trace metals such as Cd, Cu, Cr, and Zn, that are preferentially concentrated into the finer, inhalable, dust fraction and, thus, could present a health hazard in the urban areas around the basalt mining zone. The implication of this observation is that use of these nanometric-sized particulates as soil fertilizer may present different health challenges to those of conventional fertilizers, inviting future work regarding the relative toxicities of these materials. Our investigation on the particle size distribution, nano-particle mineralogy and chemical composition in typical BDW samples highlights the need to develop cleaning procedures to minimize exposure to these natural fertilizing basalt dust wastes and is, thus, of direct relevance to both the industrial sector of basalt mining and to agriculture in the region.

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Two pre-Hispanic mummies from the Andean coast, belonging to a corpus of 16 mummies from the San Miguel de Azapa (Arica, Chile), were radiocarbon dated and analyzed in order to replace them in their historical context and to study the conservation state of the hair fibers and the heavy metal presence. The radiocarbon dating placed both mummies in the Formative period (1700 years BC to 500 years AD). Global and elemental analyses were performed using scanning electron microscopy coupled with energy dispersive X-ray spectroscopy and using X-ray fluorescence spectroscopy. These combined techniques enabled to prove the good global conservation state of the mummies' hair and to detect iron, lead, bromide and also arsenic in some cases, in significant amounts inside the hair fibers. Fourier transformed infra-red spectroscopy seemed to prove the good conservation state of the hair surface at a structural level that is why the conservation of hair proteins at a molecular level will be investigated by a proteomics approach in future work.

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Piper L. (Piperaceae) is monophyletic, with species of difficult taxonomic distinction, and thus tools that facilitate interspecific identification are needed. The aims of this study were to describe the macropatterns and characterize in situ the chemical composition of leaf and stem crystals of Piper arboreum Aubl. var. arboreum, P. callosum Ruiz & Pav. and P. tuberculatum Jacq., in order to evaluate the use of the crystals on interspecific distinction. Samples were submitted to analyses under light and scanning electron microscopies, energy-dispersive x-ray spectroscopic microanalyses, and histochemical tests. We observed cuneiform, tabular, cubic, and bipiramidal prismatic crystals; raphides; styloids; blocky crystal druses; styloid crystal rosettes; and crystal concretions. We described 15 crystal macropatterns, which were distributed along three categories. The crystals were chemically classified as: pure calcium oxalate; and mixtures of oxalates and sulfates, and of oxalates, sulfates and silica. Crystal rosettes, silicified crystal concretions, and 14 out of the 15 macropatterns described are unpublished reports on biomineral inclusions in Piper and Piperaceae. The stem and leaf crystal macropatterns observed are constitutive and useful for interspecific separation of the studied species. Moreover, the crystals present relevant functions for the autecology of the analyzed taxa from Piper.

Piper L. (Piperaceae) é monofilético, com espécies de difícil distinção taxonômica, sendo necessários ferramentas que auxiliem a identificação interespecífica. Os objetivos do trabalho foram descrever os macropadrões e caracterizar in situ a composição química dos cristais caulinares e foliares de Piper arboreum Aubl. var. arboreum, P. callosum Ruiz & Pav. e P. tuberculatum Jacq., visando avaliar o uso dos cristais para a separação interespecífica. Para tanto, amostras foram submetidas à análise em microscopias de luz e eletrônica de varredura, microanálises espectroscópicas de raios-X por dispersão de energia e testes histoquímicos. Foram observados cristais prismáticos cuneiformes, tabulares, cúbicos e bipiramidais; ráfides; estiloides; drusas de cristais em bloco; rosetas cristalinas de estiloides e concrescências cristalinas. Foram descritos 15 macropadrões cristalinos reunidos em três categorias. Os cristais foram classificados quimicamente como: puros de oxalato de cálcio e misturas entre oxalatos e sulfatos e entre oxalatos, sulfatos e sílica. Rosetas cristalinas, concrescências cristalinas silicificadas e 14 dos 15 macropadrões cristalinos descritos são registros inéditos para inclusões biominerais de Piper e Piperaceae. Os macropadrões cristalinos caulinares e foliares observados são constitutivos e úteis à separação interespecífica das espécies estudadas. Ademais, os cristais desempenham funções relevantes para a autoecologia dos taxa de Piper analisados.