Anthracological study of a Chalcolithic funerary deposit from Perdigões (Alentejo, Portugal): A new analytical methodology to establish the wood burning temperature.

Anthracological analyses of charcoal samples retrieved from Pit 16 of Perdigões (Reguengos de Monsaraz, Portugal), a secondary deposition of cremated human remains dated back to the middle of the 3rd millennium BC, enabled the identification of 7 different taxa: Olea europaea, Quercus spp. (evergreen), Pinus pinaster, Fraxinus cf. angustifolia, Arbutus unedo, Cistus sp. and Fabaceae. All taxa are characteristic of both deciduous and evergreen Mediterranean vegetation, and this data might indicate that the gathering of woods employed for the human cremation/s occurred either on site, or in its vicinity. However, considering both the large distribution of the identified taxa and data about human mobility, it is not possible to conclusively determine the origin of the wood used in the cremation(s). Chemometric analysis were carried out to estimate the absolute burning temperature of woods employed for the human cremation/s. An in-lab charcoal reference collection was created by burning sound wood samples of the three main taxa identified from Pit 16, Olea europaea var. sylvestris, Quercus suber (evergreen type) and Pinus pinaster, at temperatures between 350 and 600 °C. The archaeological charcoal samples and the charcoal reference collection were chemically characterized by using mid-infrared (MIR) spectroscopy in the 1800-400 cm-1 range, and Partial Least Squares (PLS) regression method was used to build calibration models to predict the absolute combustion temperature of the archaeological woods. Results showed successful PLS forecasting of burn temperature for each taxon (significant (P <0.05) cross validation coefficients). The anthracological and chemometric analysis evidenced differences between the taxa coming from the two stratigraphic units within the Pit, SUs 72 and 74, suggesting that they may come from two different pyres or two different depositional moments.

Spatial and Temporal Distribution of the Multi-element Signatures of the Estuarine Non-indigenous Bivalve Ruditapes philippinarum.

Filter-feeder bivalves such as non-indigenous Ruditapes philippinarum absorb and accumulate metals, resulting in multi-element profiles. The goal of this study was to analyse spatial and temporal distributions of the multi-element signatures in R. philippinarum populations of the Tagus and Sado estuaries (SW coast, Portugal). The clam and sediment samples were collected at three sampling sites in each estuary, on three sampling occasions, and the analysis were done by ICP-MS (inductively coupled plasma mass spectrometry). The chemical elements were categorized according to estuarine geomorphology sources (Se, Co, Ni and Cu), elements with function in metabolic processes of the clams (Mn, Fe, Zn and Cr) and elements derived from the anthropogenic inputs (As, Pb and Cd). Zinc, Co, Ni and Pb were the main contributors for the chemical signatures of Tagus estuary populations, whilst for the Sado estuary populations were Cu, Fe, Cr, As and Cd. They were representative of all elemental categories and proved to be spatial and temporal habitat discriminators of bivalves' estuarine populations. The multi-element signatures of R. philippinarum as a natural tag derived from the physical and chemical conditions of its habitat is a potential rapid tool to use in ecological monitoring and habitat assessment.

Comparative Study of the Antioxidant and Enzyme Inhibitory Activities of Two Types of Moroccan Euphorbia Entire Honey and Their Phenolic Extracts.

Honey is a natural food product very famous for its health benefits for being an important source of antioxidant and phenolic compounds. Euphorbia honeys obtained from different regions of Morocco were evaluated for their ability to inhibit acetylcholinesterase, lipoxygenase, tyrosinase and xanthine oxidase activities. Their antioxidant properties were evaluated using the: 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical-scavenging capacity, nitric oxide scavenging activity (NO) and scavenging ability of superoxide anion radical. Then, the phenolic extracts of the same entire honey samples were evaluated by liquid chromatography coupled to diode array detection and mass spectrometry (LC-DAD-MS) and tested for the biological activities previously evaluated on the entire honeys, in order to conduct a comparative study between both (honey and phenolic extracts). The chromatographic profiles for the studied Euphorbia honey extracts were different. Phenolic compounds gallic acid, 4-hydroxybenzoic acid and p-coumaric acid were detected in all samples, whereas kampferol was only present in two samples. Physicochemical parameters and total phenolic content were also determined. Entire honey that recorded the highest rate of phenols was sample M6 (E. resinifera) = 69.25 mg GAE/100 g. On the other hand, the phenolic extracts had better antioxidant and enzyme inhibitory activities than the entire honeys, regardless the monofloral honey type. In conclusion, the studied Euphorbia honeys may have a great potential as antioxidant, anti-inflammatory and anti-tyrosinase sources for pharmaceutical and cosmetic applications.

Combination of Stable Isotope Analysis and Chemometrics to Discriminate Geoclimatically and Temporally the Virgin Olive Oils from Three Mediterranean Countries.

The knowledge of the isotopic composition of virgin olive oil (VOO) allows the evaluation of authenticity and geographical origin, being an important tool against fraud. This study aimed to assess if VOOs produced in three Mediterranean regions could be discriminated on the basis of multivariate statistical analysis of geoclimatic and isotopic data. A total of 138 geo-referenced VOO samples from Portugal, France and Turkey from two different cultivation years were collected. The isotopic composition (δ13C, δ2H and δ18O) of VOOs was obtained using an elemental analyzer coupled to an isotope ratio mass spectrometer (EA-IRMS). One-way analysis of variance for δ13C, δ2H and δ18O showed some significant differences either between crop years or geoclimatic conditions. Based on multiple regression analyses using meteorological and geographical parameters, a meteoric water line for olive oil from Portugal, France and Turkey, in two harvest years, were created to assess the impact of climate change on their δ2H and δ18O values. Principal component analysis and Linear Discriminant Analysis, used to sort samples according to geoclimatic origin, performed best for French and Portuguese olive oils. In light of the results, multivariate isotopic analysis of VOO samples may discriminate not only between geoclimatic regions but also among cultivation years.

Analytical characterization of the palette and painting techniques of Jorge Afonso, the great 16th century Master of Lisbon painting workshop.

In this work, a study on a set of paintings from the most significant altarpiece assigned to Master Jorge Afonso (c. 1470-1540) painting workshop is presented. This altarpiece is composed by fourteen paintings made to the church of Convento de Jesus, in Setúbal, Portugal, and was made circa 1517-19/1530, according to art-history. This set of paintings is compared to one of the other most important Portuguese altarpieces from the 16th century: the panels of the Round Church of the Convento de Cristo, in Tomar, made circa 1510-1515. The aim of this study is to characterize the wooden support, pigments, ground layers materials and technique used in Jorge Afonso workshop by means of complementary analyses. A dendrochronological approach was made in order to corroborate (or not) the historical date initially assigned. Infrared photography (IRP) and reflectography (IRR) allowed the study of the underdrawing technique and macro photography (MP) was used to recognize overlapping layers technique. Cross-sections from the paintings were examined by optical microscopy (OM), and analyzed by µ-X-ray diffraction (µ-XRD), Energy Dispersive X-ray Fluorescence spectroscopy (EDXRF), Scanning Electron Microscopy with Energy Dispersive X-ray Spectroscopy (SEM-EDS), micro-Raman spectroscopy (µ-Raman), micro-Fourier Transform Infrared spectroscopy (µ-FTIR), Pyrolysis Gas Chromatography Mass Spectrometry (py-GC/MS). The characterization of the palette and ground layers and the study of the overlapping of paint layers brought a new insight of the adopted painting techniques by the most important group of painters working in Portugal in the 16th century - the Lisbon workshop, leaded by Master Jorge Afonso.

Extracting natural dyes from wool--an evaluation of extraction methods.

The efficiency of eight different procedures used for the extraction of natural dyes was evaluated using contemporary wool samples dyed with cochineal, madder, woad, weld, brazilwood and logwood. Comparison was made based on the LC-DAD peak areas of the natural dye's main components which had been extracted from the wool samples. Among the tested methods, an extraction procedure with Na(2)EDTA in water/DMF (1:1, v/v) proved to be the most suitable for the extraction of the studied dyes, which presented a wide range of chemical structures. The identification of the natural dyes used in the making of an eighteenth century Arraiolos carpet was possible using the Na(2)EDTA/DMF extraction of the wool embroidery samples and an LC-DAD-MS methodology. The effectiveness of the Na(2)EDTA/DMF extraction method was particularly observed in the extraction of weld dye components. Nine flavone derivatives previously identified in weld extracts could be identified in a single historical sample, confirming the use of this natural dye in the making of Arraiolos carpets. Indigo and brazilwood were also identified in the samples, and despite the fact that these natural dyes were referred in the historical recipes of Arraiolos dyeing, it is the first time that the use of brazilwood is confirmed. Mordant analysis by ICP-MS identified the widespread use of alum in the dyeing process, but in some samples with darker hues, high amounts of iron were found instead.

Removal of pharmaceuticals in microcosm constructed wetlands using Typha spp. and LECA.

Microcosm constructed wetlands systems established with a matrix of light expanded clay aggregates (LECA) and planted with Typha spp. were used to evaluate their ability to remove pharmaceuticals ibuprofen, carbamazepine and clofibric acid from wastewaters. Seasonal variability of these systems' performances was also evaluated. Overall, removal efficiencies of 96%, 97% and 75% for ibuprofen, carbamazepine and clofibric acid, respectively, were achieved under summer conditions after a retention time of 7 days. In winter, a maximum loss of 26% in removal efficiency was observed for clofibric acid. Removal kinetics was characterized by a fast initial step (>50% removal within 6h) mainly due to adsorption on LECA but, on a larger timescale, plants also contributed significantly to the system's performance. Despite the fact that further tests using larger-scale systems are required, this study points to the possible application of these low-cost wastewater treatment systems for dealing with pharmaceuticals contaminated wastewater.