Luís Dias

Degradation of terbuthylazine, difenoconazole and pendimethalin pesticides by selected fungi cultures

Contamination of waters by xenobiotic compounds such as pesticides presents a serious environmental problem with substantial levels of pesticides now contaminating European water resources. The aim of this work was to evaluate the ability of the fungi Fusarium oxysporum, Aspergillus oryzae, Lentinula edodes, Penicillium brevicompactum and Lecanicillium saksenae, for the biodegradation of the pesticides terbuthylazine, difenoconazole and pendimethalin in batch liquid cultures. These pesticides are common soil and water contaminants and terbuthylazine is considered the most persistent triazine herbicide in surface environments. P. brevicompactum and L. saksenae were achieved by enrichment, isolation and screening of fungi capable to metabolize the pesticides studied. The isolates were obtained from two pesticide-primed materials (soil and biomixture). Despite the relatively high persistence of terbuthylazine, the results obtained in this work showed that the fungi species studied have a high capability of biotransformation of this xenobiotic, comparatively the results obtained in other similar studies. The highest removal percentage of terbuthylazine from liquid medium was achieved with A. oryzae (~80%), although the major biodegradation has been reached with P. brevicompactum. The higher ability of P. brevicompactum to metabolize terbuthylazine was presumably acquired through chronic exposure to contamination with the herbicide. L. saksenae could remove 99.5% of the available pendimethalin in batch liquid cultures. L. edodes proved to be a fungus with a high potential for biodegradation of pesticides, especially difenoconazole and pendimethalin. Furthermore, the metabolite desethyl-terbuthylazine was detected in L. edodes liquid culture medium, indicating terbuthylazine biodegradation by this fungus. The fungi strains investigated could prove to be valuable as active pesticide-degrading microorganisms, increasing the efficiency of biopurification systems containing wastewaters contaminated with the xenobiotics studied or compounds with similar intrinsic characteristics.

Interaction between water soluble and volatile compounds of Cistus ladanifer L.

SummaryPhytotoxic activity of single and combined application of water soluble and volatile compounds of Cistus ladanifer on germination and early root growth of subterranean clover was investigated. Total germination, lag and speed of germination were both inhibited and stimulated, with the activity of volatiles on total germination depending upon the presence of water solubles. Antagonism between water solubles and volatiles was always found, resulting in a reduction of inhibition or a shift from inhibition to stimulation. It is suggested that the simultaneous presence of water solubles and volatiles might result in changes of the chemical nature of metabolites released by C. ladanifer. Early root growth was always inhibited but only by water solubles, and no interaction was found. The ecological implications of these results are discussed in terms of the exhaustion of competitors seedbanks by a two-step process in which germination is less inhibited or even stimulated by water solubles and volatiles, followed by a stronger and volatiles-independent inhibition of early root growth.

Characterization of glue sizing under calcium carbonate ground layers in Flemish and Luso-Flemish painting – analysis by SEM-EDS, μ-XRD and μ-Raman spectroscopy

This work regards the study of painting techniques in Portuguese workshops of the 15th and early 16th centuries, specifically addressing the methodology used on the preparation of ground layers. The influence of Flemish painting in Portugal is evident in stylistic and iconographic themes of that period. As regards the painting materials, we confirmed that this influence also extended to the ground layer technique. The use of a sizing layer with calcium sulphate or garlic to isolate the support from the calcium carbonate layer was verified by SEM-EDS but not confirmed by μ-XRD or μ-Raman spectroscopy. This work is part of a larger project, “The invisible ground layer and its influence in Portuguese paintings from the 15th and 16th centuries: a question to be settled”.

Characterization of Glue Sizing Layers in Portuguese Wood Paintings from the 15th and 16th Centuries by SEM Secondary Electron Images and μ-FTIR

According to treatises on 15th and 16th century paintings, artists dedicated particular attention to the sizing layer-consisting mainly of animal glue applied onto the wood support before further application of the ground layer. The stability of a painting mainly depends on the presence of a very cohesive sizing layer. However, the study of these layers has not received special attention from researchers. In this article we present a methodology for characterization of the sizing layer both chemically, by IR spectroscopy (Fourier transform infrared spectroscopy), and morphologically, by scanning electron microscopy (SEM). Secondary electron images obtained by SEM allow precise characterization of such layers. Painting reconstructions were used as references in development of the method to study the sizing layer in real painting samples. Presented herein are examples of this study on 15th and 16th century Portuguese paintings, particularly on the Triptych of S. Simão, from the Aveiro Museum, and S. Pedro, belonging to the Mercy of Tavira.

Multianalytical approach for the authenticity of an eighteenth-century Pascal Taskin harpsichord

This paper surveys a detailed characterization of a prestigious harpsichord brought into fashion in 1782 by Pascal Taskin. The implemented analytical methodology required the use of in situ Energy Dispersive X-Ray Fluorescence (EDXRF) for elemental analysis of the color palette, optical and SEM imaging (SE and BSE modes) for the layered structure identification, Scanning Electron Microscopy coupled with Energy Dispersive Spectroscopy (SEM-EDS) for elemental composition of the inorganic compounds, Fourier Transform Infrared (FTIR) spectroscopy for some binders and THM-GC/MS as well for resinous layers identification. By cross-checking these data with those obtained by digital radiography, it was concluded that a true ravalement of the harpsichord was in fact undertaken and that, among more than five interventions applied to the instrument until the present day, the third one may correspond to the one performed at Pascal Taskins time.

GREGÓRIO LOPES painting workshop: characterization by X-ray based techniques. Analysis by EDXRF, μ-XRD and SEM-EDS

Gregorio Lopes is one of the most famous Portuguese painters of the 15th–16th centuries. This work is a contribution to the study of his painting technique, specifically addressing the methodology used in the preparation of ground layers, which has never been carried out previously with this multianalytical method. For this purpose characterization of the ground layers of a selection of his paintings was carried out by micro-Energy Dispersive X-ray Fluorescence spectroscopy (μ-EDXRF), micro-X-ray Diffraction (μ-XRD), Scanning Electron Microscopy - Energy Dispersive Spectroscopy (SEM-EDS) and complemented by micro-Raman spectroscopy. This work presents the results obtained on two altarpieces (c.1544) produced at the same period by this Portuguese artist. Ground layers are composed mainly of calcium sulfate — anhydrite and gypsum — and other compounds such as dolomite. Reference samples were prepared to obtain diffraction pattern of different percentage of gypsum and anhydrite and compared with the results from historical samples.

Modeling Size‐number Distributions of Seeds for Use in Soil Bank Studies

Knowledge of soil seed banks is essential to understand the dynamics of plant populations and communities and would greatly benefit from the integration of existing knowledge on ecological correlations of seed size and shape. The present study aims to establish a feasible and meaningful method to describe size-number distributions of seeds in multi-species situations. For that purpose, size-number distributions of seeds with known length, width and thickness were determined by sequential sieving. The most appropriate combination of sieves and seeds dimensions was established, and the adequacy of the power function and the Weibull model to describe size-number distributions of spherical, non-spherical, and all seeds was investigated. We found that the geometric mean of seed length, width and thickness was the most adequate size estimator, providing shape-independent measures of seeds volume directly related to sieves mesh side, and that both the power function and the Weibull model provide high quality descriptions of size-number distributions of spherical, non-spherical, and all seeds. We also found that, in spite of its slightly lower accuracy, the power function is, at this stage, a more trustworthy model to characterize size-number distributions of seeds in soil banks because in some Weibull equations the estimates of the scale parameter were not acceptable.

Investigating and modeling the combined effects of pH and osmotic pressure on seed germination for use in phytoactivity and allelopathic research

Abstract Phytoactivity and allelopathic studies are heavily dependent on germination bioassays of water solutions of allelochemical(s), which necessarily imply that pH and osmotic pressure vary among treatments and between treatments and controls and are therefore a confounding factor in the assessment of seed germination responses to allelochemical(s). When the contribution of pH and osmotic pressure to seed germination responses is considered in experimental designs their effects are almost without exceptions examined separately being assumed, without any evidences, that pH and osmotic pressure act independently on seed germination responses. The objectives of this work were to examine experimentally such assumption using wheat, lettuce, and subterranean clover cultivars to evaluate and model the combined effects on germination of pH and osmotic pressure in the range between 3.0–6.0 and 0–100 mOsmol kg−1, respectively. Empirical equations are fitted, discussed, and the need to consider the simultaneous effects of pH and osmotic pressure firmly established. Finally, the use of the equations fitted and its impact on conclusions is exemplified in a dose-response bioassay of water extracts of Cistus ladanifer on seed germination using subterranean clover as target species where hormesis was found before allelochemical effects were corrected for pH and osmotic pressure values of control and extracts.

Natural limestone discolouration triggered by microbial activity—a contribution

Colour is a major argument that drives the decision of an architect in a specific architecture project and one of the most important characteristics and perceptible aspects of natural building stones. “Blue” limestones are building rocks, with different geological ages, typically used in several countries, and are known for their vulnerability to alteration, which causes colour change and the occurrence of unaesthetic patterns. Owing to this vulnerability, the conservation-restoration works in monuments, or new buildings constructed with “blue” limestone is extremely costly. Considering that the main limitation of this lithological variation is the chromatic change, a multidisciplinary approach was envisaged in this study to allow a closer insight into the chemical and mineralogical alterations and the microbial communities. Results obtained suggest that the inorganic alteration in the “blue” limestone may create favourable conditions for microbial growth and could lead to an increment in deterioration process.

Challenging wax-cast figurine serial production unravelled by multi-analytical techniques

Eight complementary techniques were successfully applied to study a pair of very alike eighteenth-century colored wax figurines belonging to the Museu Nacional Machado de Castro, Coimbra (Portugal): examination under visible and ultraviolet light, X-ray radiography (XRR), neutron radiography and tomography (NR and NT), energy dispersive X-ray fluorescence (EDXRF), scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDS), micro-X-ray diffraction (μ-XRD), gas chromatography coupled with mass spectrometry (GC/MS) and micro-confocal Raman spectroscopy (μ-Raman). A careful examination of the two objects provided an insight into their manufacturing and revealed that they were cast from the same molds, although details differ. The main cast material employed was a mixture of beeswax, Venice turpentine, other diterpenoid resins and a very low amount of lipids. The wax used was certainly reclaimed from a metallurgic activity involving lost-wax casting. Each figurine consists of sixteen parts, most of which consist of solid wax. The presence of fillings within the body was unexpected. The elements which remained hollowed played a fundamental role at the assembling stage. A loose wooden tenon helped to keep the head in place and metal rods were used to fasten the base to the main body. Polychromy was carried out in wax, with different pigments and opacifiers. The fabrication of the colored wax from different inorganic/organic wastes is also discussed. Textures were achieved by adding materials. The results gathered offered the unique opportunity to verify aspects inherent to the production of multiple copies in wax casting.