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  • Chemistry Centre of Minho University
    Campus de Gualtar
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Chromatographic techniques are gaining interest among the archaeological community as they allow the identification of organic residues from archaeological materials, an important source of information for archaeologists. These are often... more
Chromatographic techniques are gaining interest among the archaeological community as they allow the identification of organic residues from archaeological materials, an important source of information for archaeologists. These are often composed of complex mixtures of molecules that need to be resolved, a crucial step in molecular archaeology to identify biomarkers and provide information on the diet of our ancestors, habits, technologies, or to follow ancient trade routes.
The target of this Special Issue is to present the state-of-the-art in analytical chromatographic studies of organic residues on archaeologic materials. Multidisciplinary projects with a broad timespan and geographical region where chromatography assumes an important role, procedures focusing on the best archaeological practices regarding organic residue studies, and experimental archaeology on searching for new biomarkers will also be valued.
This research aimed to determine the origin of organic residues from funerary contexts in the El Caño settlement (Gran Coclé area, Panamá, Central America) by means of multiple molecular probing techniques (GC-MS of organic solvent... more
This research aimed to determine the origin of organic residues from funerary contexts in the El Caño settlement (Gran Coclé area, Panamá, Central America) by means of multiple molecular probing techniques (GC-MS of organic solvent extracts and pyrolysis-GC-MS, THM-GC-MS and FTIR of solid samples). The samples include particles of precious resin figurines, fillings of golden objects, tomb sediments, plant exudates from extant plants (reference collection) and other reference materials (amber). The labdane diterpene fingerprints (eperuic, iso-ozic, copalic and kolavenic acids and derivatives) of the resin figurines, a resinous bead and several other samples, suggest that they were composed primarily of Hymenaea resin. Besides traditional interpretation approaches (visual comparison of chromatograms and relative proportions data), we used a novel OpenChrom® application that resolves complex pyrolysis chromatograms by screening data from archaeological samples for marker products defined on the basis of a reference collection (ChromIdent). ChromIdent confirmed the Hymenaea origin of many samples and also Burseraceae resin was identified in some samples, which is present as a minor ingredient in resin figurines (indicative of mixing practices) and as the dominant resin in tomb sediment that had been in contact with the corpses (indicating balsaming practices). The degree of polymerization of the Hymenaea resin was higher than for extant resin but diagenetic alteration (especially condensation of cyclic moieties) was much smaller than for amber, implying that the manufacturers used resin (or copal), not amber. These results were confirmed by FTIR, which allowed identification of non-fossil Hymenaea resin as the main constituent of one of the resin figurines. Several golden object infillings contained wax derivatives, probably beeswax, accompanied by various types of plant resin, which may well indicate the use of meliponines' cerumen for manufacturing (lost-wax casting). The findings highlight the potential of complementary molecular techniques to resolve questions on materials and manufacturing of archaeological artefacts, and the need for cross-comparison of molecular and ethnographic information in the study of archaeobotanical remains and the processes involved in their management.
The colourant composition of a northern Portugal megalithic barrow decorated with ‘solar’ motifs was studied using a multi-analytical approach, allowing the characterisa- tion of the painting techniques, pigments and binders. The red... more
The colourant composition of a northern Portugal megalithic barrow decorated with ‘solar’ motifs was studied using a multi-analytical approach, allowing the characterisa- tion of the painting techniques, pigments and binders. The red pigment was prepared with iron oxide minerals, using vegetal oils as organic additives, while the black pigment was char- coal without any organic additives or binders. The solar motif was first drawn with charcoal and subsequently painted with a red pigment.
Research Interests:
The colourant composition of a northern Portugal megalithic barrow decorated with 'solar' motifs was studied using a multi-analytical approach, allowing the characterisa-tion of the painting techniques, pigments and binders. The red... more
The colourant composition of a northern Portugal megalithic barrow decorated with 'solar' motifs was studied using a multi-analytical approach, allowing the characterisa-tion of the painting techniques, pigments and binders. The red pigment was prepared with iron oxide minerals, using vegetal oils as organic additives, while the black pigment was charcoal without any organic additives or binders. The solar motif was first drawn with charcoal and subsequently painted with a red pigment.
Neste estudo apresentam-se os resultados das análises por Cromatografia Gasosa com Espectrometria de Massa acoplada (GC/MS) aos resíduos orgânicos presentes em contentores cerâmicos como ânforas, potes meleiros e colmeias. A interpretação... more
Neste estudo apresentam-se os resultados das análises por Cromatografia Gasosa com Espectrometria de Massa acoplada (GC/MS) aos resíduos orgânicos presentes em contentores cerâmicos como ânforas, potes meleiros e colmeias. A interpretação dos resultados obtidos permitiu revelar pistas sobre o conteúdo original destes contentores.
Honey was the main sweetener substance of the ancient world, being repeatedly mentioned in the literary sources and directly or indirectly well documented by archaeology throughout the Mediterranean basin. This study presents the results... more
Honey was the main sweetener substance of the ancient world, being repeatedly mentioned in the literary sources and directly or indirectly well documented by archaeology throughout the Mediterranean basin.
This study presents the results of gas chromatography coupled with mass spectrometry (GC / MS) analyses of organic residues in ceramic honeypots and beehives from the Augustan period. The results obtained allowed the identification of chemical compounds characteristic of honey and honey products.
The organic content of three ceramic vases uncovered in the megalithic tomb of Currais do Galhordas (Central Eastern Portugal) – a monument built in the second half of the 4th millennium cal BC and reused in the 3th and in the 2nd... more
The organic content of three ceramic vases uncovered in the megalithic tomb of Currais do Galhordas (Central Eastern Portugal) – a monument built in the second half of the 4th millennium cal BC and reused in the 3th and in the 2nd millennia cal BC – was analysed by gas-chromatography with mass detection. The vases are allegedly connected with the latest use of the monument, during the Bronze Age (2nd millennium cal BC). Two of them presented traces of grapes or red fruits, together with fish; the third vase exhibited animal fat remains, possibly milk, associated with plant oils. Our results are compatible with other data from Iberian archaeological sites of identical period, in some cases located relatively close to the megalithic tomb of Currais do Galhordas.
The oxytocinergic system is a primary biological system involved in regulating a child's needs for bonding and for protection from threats. It is responsive to social experiences in close relationships, though evidence across studies is... more
The oxytocinergic system is a primary biological system involved in regulating a child's needs for bonding and for protection from threats. It is responsive to social experiences in close relationships, though evidence across studies is not entirely consistent. Guided by previous literature, we investigated individual and environmental factors predicting and presumably affecting children's oxytocin (OT) response during mother-child interaction. by focusing on children's OXTR genotype, and maternal behavior, respectively. This was achieved by assessing salivary OT levels of 88 Portuguese preschoolers prior to and following a mother-child interaction task, and by genotyping children's OXTR SNP rs53576. Maternal interactive behavior was assessed using Ainsworth scales. Results indicated that child genotype and mother's sensitive responsiveness interacted in predicting change in child OT concentrations from before to after the interaction. Specifically, Genotypic differences emerged under conditions of low maternal sensitive responsiveness: OT levels increased over time for children with the GG genotype when maternal sensitive responsiveness was low, but no such genotypic differences were evident when mothers were highly sensitive responsive. Findings provide preliminary support for the notion that increased understanding of children's OT and close relationships requires consideration of both individual and environmental factors.
Limited information exists on the bioaccessibility and intestinal uptake of essential minerals from different types of beans cooked through different cooking methods. This study aimed to estimate the in vitro bioaccessibility and intestinal... more
Limited information exists on the bioaccessibility and intestinal uptake of essential minerals from different types of beans cooked through different cooking methods. This study aimed to estimate the in vitro bioaccessibility and intestinal uptake of the essential minerals K, Ca, Mg, Fe, Zn, Mn, Cu and Mo from four different types of beans (kidney, black, white and cowpea) cooked under different conditions (home-cooked and industrially processed canned product). Results showed that the bioaccessibility and uptake of most essential minerals is higher in
canned beans. Mn was the mineral that presented the highest bioaccessibility (43–63%), and Mo had the lowest (3–36%). The highest uptake was observed for Mg (59.9%), while the lowest was found for Fe (10.5%).
Regarding the type of beans, white beans presented the highest bioaccessibility and uptake for all the analyzed essential minerals and thus its consumption is preferable from a nutritional point of view.
Research Interests:
Honey was the main sweetening agent in the ancient world; it is mentioned in literary sources and archaeologically documented all over the Mediterranean basin. Its production extended throughout different parts of the Roman Empire, with... more
Honey was the main sweetening agent in the ancient world; it is mentioned in literary sources and archaeologically documented
all over the Mediterranean basin. Its production extended throughout different parts of the Roman Empire, with important economic impacts on family economies, both as a foodstuff and as a commercial product. This paper focuses on the chromatographic analysis of Roman Iberian honeypots and ceramic beehives, identifying tracer characteristics from ancient honey in sherds from seven honeypots and three beehives. The obtained results present an important contribution to the knowledge of the local Roman Iberian economy, particularly relating to the production, transport and trade of honey in locally manufactured ceramic containers.
Research Interests:
Como parte del estudio de los objetos arqueológicos del sitio arqueológico de El Caño (provincia de Coclé, Panamá), hemos creado una colección de referencia de elementos de la vegetación local que son particularmente prolíficos en... more
Como parte del estudio de los objetos arqueológicos del sitio arqueológico de El Caño (provincia de Coclé, Panamá), hemos creado una colección de referencia de elementos de la vegetación local que son particularmente prolíficos en exudados (resinas y gomas). Estas muestras fueron analizadas por cromatografía de gases en combinación con espectrometría de masas (GC-MS, después de disolución e inyección), y también por la introducción de muestras sólidas seguida de pirólisis analítica (Py-GC-MS y THM-GC-MS). De las 11 muestras de la colección referencia podría ser sencillo distinguir a diferentes niveles de información molecular: i) materiales resinosos vs. gomas, ii) distribución de terpenos (monoterpenos, sesquiterpenos, diterpenos, triterpenos) para resinas o contribuciones de proteínas/taninos/polisacáridos/látex para las gomas; y iii) biomarcadores específicos (estructuras biomoleculares que todavía no han sido identificadas). En el trabajo también se presentan algunos de los resultados obtenidos del análisis de muestras arqueológicas. Una de las figuras de resina parece estar principalmente formada por resinas de las cuales los derivativos de ácido labdánico sugieren de forma sólida que son originarios de resina de Hymenaea. La resina parece estar afectada por fosilización (condensación), lo que implica que estamos ante ámbar. Otras muestras estaban constituidas por ceras y materiales inorgánicos.
A Arqueometria é uma ciência multidisciplinar que visa o estudo dos artefactos arqueológicos, complementando os trabalhos arqueológicos com evidências científicas. A colaboração entre Químicos e Arqueólogos é antiga, sendo a utilização de... more
A Arqueometria é uma ciência multidisciplinar que visa o estudo dos artefactos arqueológicos, complementando os trabalhos arqueológicos com evidências científicas. A colaboração entre Químicos e Arqueólogos é antiga, sendo a utilização de técnicas cromatográficas para a análise de resíduos orgânicos presentes em materiais arqueológicos uma das facetas mais visíveis dessa colaboração. De facto, a elevada porosidade de alguns materiais arqueológicos, como as cerâmicas, permite guardar no seu interior vestígios das matrizes orgânicas com as quais estiveram em contacto, o que possibilita a sua análise posterior por técnicas cromatográficas hifenadas, a deteção de traçadores moleculares e a identificação dos resíduos orgânicos.
Research Interests:
Foi identificada, no conjunto de ânforas da cidade romana de Conimbriga, uma produção, de cariz regional, de uma classe de ânforas que não se encontra descrita na bibliografia. Esta produção é caracterizada quanto à sua morfologia e... more
Foi identificada, no conjunto de ânforas da cidade romana de Conimbriga, uma produção, de cariz regional, de uma classe de ânforas que não se encontra descrita na bibliografia.
Esta produção é caracterizada quanto à sua morfologia e fabrico (regional), proposta a localização genérica do centro de produção (norte da Lusitânia, verosimilmente no Baixo Mondego) e são feitas propostas quanto à sua cronologia e utilização (ânfora vinária dos séculos I a III d.C.).
Research Interests:
This paper present the results of the study of two roman Baetican shipwrecks and a fishery trap discovered in the coastal zone of Esposende (North Portugal). Those findings were possible due to particular meteorological and hydrological... more
This paper present the results of the study of two roman Baetican shipwrecks and a fishery trap discovered in the coastal zone of Esposende (North Portugal). Those findings were possible due to particular meteorological and hydrological conditions responsible for a strong sand loss on the beach and the subsequent exhumation of former sedimentary deposits.
Research Interests:
In this study we present amphorae of the Augustan era collected in Portugal and in Galicia revealing that they were not a ‘premature’ or ‘experimentation’ production but the result of a complementary phenomenon related to products from... more
In this study we present amphorae of the Augustan era collected in Portugal and in Galicia revealing that they were not a ‘premature’
or ‘experimentation’ production but the result of a complementary phenomenon related to products from Baetica.
Taking into account the growing interest in the theme of amphora contents, analysis of organic residues present in Lusitanian amphorae
by Gas Chromatography coupled with Mass Spectrometry (GC/MS) were conducted. The results obtained revelatory clues about the
original contents of these amphorae.
Research Interests:
Discoveries in the mouth of Peralto stream (Esposende, Northern Portugal) revealed traces of Roman occupation along the Iberian Atlantic coast. Among them were found a large number of ceramic container fragments from Baetica region... more
Discoveries in the mouth of Peralto stream (Esposende, Northern Portugal) revealed traces of Roman occupation along the Iberian Atlantic coast. Among them were found a large number of ceramic container fragments from Baetica region (ancient Roman province in Hispania under the influence of the Guadalquivir River basin, nowadays
Andaluzia) from a shipwreck dating from the time of Augustus. Some questions were raised about the type of cargo in the ship. The discovery was an opportunity for an exciting and fruitful collaboration between chemists and archaeologists.
This paper presents some introductory concepts on the chemical analysis of ceramic artifacts.
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We have determined the composition of rock art pigments from two megalithic barrows located in the north of Portugal. The use of XRD, SEM–EDS and FT–IR spectroscopy confirmed the presence of hematite and kaolinite in the red pigments from... more
We have determined the composition of rock art pigments from two megalithic barrows located in the north of Portugal. The use of XRD, SEM–EDS and FT–IR spectroscopy confirmed the presence of hematite and kaolinite in the red pigments from the Eireira barrow, and kaolinite in the white pigment from the Leira das Mamas barrow. The organic composition of the pigments was studied by GC–MS, suggesting that the red sinuous lines and dots from the Eireira barrow were prepared with cooked or heated algae and/or aquatic plants, with egg as binder, while the white pigment from the Leira das Mamas barrow revealed a mixture of vegetable oils for kaolinite moulding, which could be stabilized by temporary exposure to high temperatures. The multi-analytical approach used on this study of megalithic pigments allowed the recovery of important data about northwestern prehistoric communities, namely the way in which they exploited existing resources and their ability to transform them.
Research Interests:
Lisbon is the capital city of Portugal with about 565,000 residents and a population density of 6,600 inhabitants per square kilometre. The town is surrounded by satellite cities, forming together a region known as "Lisbon... more
Lisbon is the capital city of Portugal with about 565,000 residents and a population density of 6,600 inhabitants per square kilometre. The town is surrounded by satellite cities, forming together a region known as "Lisbon Metropolitan Area" with about 3 million inhabitants. It is estimated that more than one million citizens come into the Lisbon area every day from the outskirts, leading to elevated traffic densities and intense traffic jams. Airborne particulate matter limit values are frequently exceeded, with important consequences on air pollution levels and obvious negative impacts on human health. Atmospheric aerosols are known to have in their structure significant amounts of carbonaceous material. The knowledge of the aerosols carbon content, particularly on their several carbon forms (as TC, EC and OC, meaning respectively Total, Elemental and Organic carbon) is often required to provide information for source attribution. In order to assess the vehicles PM input...
Research Interests:
The particulate emissions from biomass burning are a growing concern due to the recent evidence of their ubiquitous and important contribution to the ambient aerosol load. A possible strategy to apportion the biomass burning share of... more
The particulate emissions from biomass burning are a growing concern due to the recent evidence of their ubiquitous and important contribution to the ambient aerosol load. A possible strategy to apportion the biomass burning share of particulate matter is the use of organic molecular tracers. Anhydrosugars (levoglucosan, mannosan and galactosan), together with two organic acids (dehydroabietic and pimaric acids), were previously reported as organic markers for particulate wood burning emissions. These five compounds were studied in four European cities (Helsinki, Copenhagen, Birmingham and Oporto), at both a Roadside and an Urban Background station, during a summer and a winter campaign in the fine (PM(2.5)) and the coarse (PM(10-2.5)) size-fractions of the ambient aerosol. Levoglucosan concentrations were highest in the city of Oporto. In winter, levoglucosan was more present in the fine fraction but in summer, concentrations were similar in both size fractions. Levoglucosan concentrations in the fine size fraction were higher in winter, but no seasonal differences were observed for the coarse size fraction. The lack of difference between the Roadside and Urban Background levoglucosan concentrations points towards a regional nature of this type of pollution. Wood burning was estimated to contribute to about 3.1% of the winter PM(10) mass in Oporto, and to 3.7% in Copenhagen. Mannosan followed the trends exhibited by levoglucosan. The ratio between the levoglucosan and mannosan concentrations allowed determination of a preference for softwood over hardwood in all four cities. Galactosan, pimaric acid and dehydroabietic acid were found to be minor compounds.
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ABSTRACT Burning of agricultural waste residue is a common method of disposal when preparing land following crop harvest. This practice introduces volatile organic compounds, including polycyclic aromatic hydrocarbons (PAHs), into the... more
ABSTRACT Burning of agricultural waste residue is a common method of disposal when preparing land following crop harvest. This practice introduces volatile organic compounds, including polycyclic aromatic hydrocarbons (PAHs), into the atmosphere. This study examines the particle size distribution in the smoke emissions of two common agricultural waste residues (biofuels) in California, almond prunings and rice straw. The residues were burned in a combustion chamber designed specifically for this purpose, and the smoke emissions were collected on 10-stage MOUDI impactors for analysis of PAH and total particle mass. The results, in units of emission factors, show that combustion temperature is an important factor in determining the smoke particle PAH composition. Total PAH emissions from rice straw burns were 18.6mgkg−1 of fuel, while the emissions from almond prunings were lower at 8.03mgkg−1. The less volatile five- and six-ring PAH was predominately on smaller particles where it condensed in the early stages of combustion while the more volatile three- and four-ring PAH formed on larger particles as the smoke cooled.
ABSTRACT An atmospheric aerosol study was performed in 2008 inside an urban road tunnel, in Lisbon, Portugal. Using a high volume impactor, the aerosol was collected into four size fractions (PM0.5, PM0.5–1, PM1–2.5 and PM2.5–10) and... more
ABSTRACT An atmospheric aerosol study was performed in 2008 inside an urban road tunnel, in Lisbon, Portugal. Using a high volume impactor, the aerosol was collected into four size fractions (PM0.5, PM0.5–1, PM1–2.5 and PM2.5–10) and analysed for particle mass (PM), organic and elemental carbon (OC and EC), polycyclic aromatic hydrocarbons (PAH), soluble inorganic ions and elemental composition. Three main groups of compounds were discriminated in the tunnel aerosol: carbonaceous, soil component and vehicle mechanical wear. Measurements indicate that Cu can be a good tracer for wear emissions of road traffic. Cu levels correlate strongly with Fe, Mn, Sn and Cr, showing a highly linear constant ratio in all size ranges, suggesting a unique origin through sizes. Ratios of Cu with other elements can be used to source apportion the trace elements present in urban atmospheres, mainly on what concerns coarse aerosol particles.
... DOI: 10.1080/00032710500317975 Ali Niazi a ... curve resolution, analysis of variance, and calibration purposes using spectrophotometric, spectrofluorimetric, chromatographic, flow injection, sensory analysis, or experimental design... more
... DOI: 10.1080/00032710500317975 Ali Niazi a ... curve resolution, analysis of variance, and calibration purposes using spectrophotometric, spectrofluorimetric, chromatographic, flow injection, sensory analysis, or experimental design data and kinetic procedures (Bro 19977. Bro ...
Particulate matter, either with aerodynamical diameter below 10 mum (PM10) or the fine (aerodynamical diameter below 2.5 mum, PM2.5) or coarse (aerodynamical diameter between 2.5 and 10 mum, PM2.5-10) modes only, are presently regarded as... more
Particulate matter, either with aerodynamical diameter below 10 mum (PM10) or the fine (aerodynamical diameter below 2.5 mum, PM2.5) or coarse (aerodynamical diameter between 2.5 and 10 mum, PM2.5-10) modes only, are presently regarded as one of the main threats to public health instigated by air pollution. The levels of ambient air particulates are regulated but the limits are frequently surpassed. It is therefore necessary to identify and quantify PM sources and their variability, as well as the biogenic processes that to some extent control their ambient load, in order to effectively regulate on the anthropogenic activities which originate PM. PM2.5-10 and PM2.5 were monitored in Oporto, NW Portugal, at two contrasting sites (directly impacted by traffic, roadside, and at the urban background) during two one-month campaigns (winter and summer). Sampling was conducted independently during daytime and night-time. Out of the 207 sampling periods analysed, 38 (18%) were above the European legal PM10 limit of 50 ?g m-3. PM2.5 concentrations above the limit of 25 ?g m-3 proposed by the EC occurred in 70 out of 202 sampling (35%). More exceedances occurred in winter than in summer and at roadside than at the urban background. Within the scope of this work, the relationship between PM concentrations, namely the occurrence of exceeding PM limit values, and meteorological variables or the sampling period (day/night, work day/weekend) and will be presented. Besides PM mass, the soluble ionic composition (Cl-, SO42-, NO3-, Na+, NH4+, K+, Ca2+ and Mg2+) as well as the elemental composition (Al, Si, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, As, Se, Br, Rb, Sr, Zr, Sn, Ba and Pb) were also determined. This allowed the application of multivariate analysis (principal component analysis with multi-linear regression analysis, PCA-MLRA, and positive matrix factorisation, PMF). Five main sources were identified in the fine and coarse modes (direct road traffic emissions, industrial activities related with refuse incineration or metallurgy, soil dust emissions, sea salt and fuel oil combustion coupled to secondary formation). The contribution of the various sources or source types to the PM load was calculated. A comparison between the relative contribution of the various sources or source types during exceeding and non-exceeding periods is conducted in order to assess if the exceeding periods may be attributed to a particular origin. Also, the concentration and relative contribution to total PM mass of the various PM constituents measured during exceedance and non-exceedance episodes is compared in order to assess their variability between the two types of events.
The recent discovery of garum1 remains in a Roman archaeological site in the south of Portugal, used for the processing and storage of fish and shellfish-based products, offers an unprecedented opportunity to pioneer biological DNA-based... more
The recent discovery of garum1 remains in a Roman archaeological site in the south of Portugal, used for the processing and storage of fish and shellfish-based products, offers an unprecedented opportunity to pioneer biological DNA-based analyses of archaeological remains, through cutting-edge analytical methods like High Throughput Sequencing (HTS). Our study seeks to reconstruct the species composition of the seafood products used in garum preparation of this region over the centuries IV and V, applying a combination of the DNA barcode approach with HTS technology. Initially, primer combinations amplifying different and short fragments (<320 bp) of the cytochrome oxidase I mitochondrial gene (COI) were tested for success in amplification of DNA
isolated from fish tissue. The most successful primer pair was then used to generate amplicons from 2 garum DNA isolates, and submitted to HTS sequencing in a GS 454 FLX Titanium platform. Probably due to the old age of the DNA under examination, only a small number of reads from each sample (<200) was eligible for analyses. These reads were compared to our local comprehensive reference libraries of annotated DNA barcodes for fish and shellfish. We found matches with between 99-100% similarity in seven different fish species. The fish species found are common in the region according to current knowledge. Replicate and additional analyses are being carried out in order to verify and deepen these findings.
Research Interests:
The recent discovery of garum remains in a Roman archaeological site in the south of Portugal, used for the processing and storage of fish and shellfish-based products, offers an unprecedented opportunity to pioneer biological DNA-based... more
The recent discovery of garum remains in a Roman archaeological site in the south of Portugal, used for the processing and storage of fish and shellfish-based products, offers an unprecedented opportunity to pioneer biological DNA-based analyses of archaeological remains, through cutting-edge analytical methods like High Throughput Sequencing (HTS).

Our study seeks to reconstruct the species composition of the seafood products used in garum preparation of this region over the centuries IV and V, applying a combination of the DNA barcode approach with HTS technology.

Initially, primer combinations amplifying different and short fragments (<320 bp) of the cytochrome oxidase I mitochondrial gene (COI) were tested for success in amplification of DNA isolated from fish tissue. The most successful primer pair was then used to generate amplicons from 2  garum DNA isolates, and submitted to HTS sequencing in a GS 454 FLX Titanium platform.

Probably due to the old age of the DNA under examination, only a small number of reads from each sample (<200) was eligible for analyses. These reads were compared to our local comprehensive reference libraries of annotated DNA barcodes for fish and shellfish.

We found matches with between 99-100% similarity in seven different fish species. The fish species found are common in the region according to current knowledge. Replicate and additional analyses are being carried out in order to verify and deepen these findings.
Research Interests:
This paper presents the results obtained through analysis carried out to organic residues present in different ceramic containers, namely in amphorae, honeypots and beehives found in the Peninsular northwest, using gas chromatography... more
This paper presents the results obtained through analysis carried out to organic residues present in different ceramic containers, namely in amphorae, honeypots and beehives found in the Peninsular northwest, using gas chromatography coupled with mass spectrometry.
Research Interests:

And 4 more

The target of this Special Issue is to present the state-of-the-art in analytical chromatographic studies of organic residues on archaeologic materials. Multidisciplinary projects with a broad timespan and geographical region where... more
The target of this Special Issue is to present the state-of-the-art in analytical chromatographic studies of organic residues on archaeologic materials. Multidisciplinary projects with a broad timespan and geographical region where chromatography assumes an important role, procedures focusing on the best archaeological practices regarding organic residue studies, and experimental archaeology on searching for new biomarkers will also be valued.
Resumo: Foram estudados por difração de raios-X (DRX) e por microscopia eletrónica de varrimento com microanálise por feixes de eletrões (MEV-EDS) fragmentos cerâmicos de ânforas Haltern 70, dolia e tipo urceus oriundos do naufrágio... more
Resumo: Foram estudados por difração de raios-X (DRX) e por microscopia eletrónica de varrimento com microanálise por feixes de eletrões (MEV-EDS) fragmentos cerâmicos de ânforas Haltern 70, dolia e tipo urceus oriundos do naufrágio Bético Augustano de Esposende. As fases cristalinas evidenciaram a presença de quartzo como o componente principal, tendo-se detetado minerais associados ao tratamento térmico dos materiais cerâmicos. A microestrutura das amostras foi mapeada por MEV e os resultados de EDS confirmaram os elementos químicos identificados por DRX. Uma análise de componentes principais permitiu concluir da existência de semelhanças na composição química de ânforas de uma mesma tipologia, sendo estas distintas para tipologias diferentes. As análises elementares efetuadas indiciam uma proveniência das cerâmicas da zona do vale do Guadalquivir. Abstract: X-ray diffraction (XRD) and scanning electron microscope equipped with energy-dispersive X-ray spectroscopy (SEM-EDS) were used to study Haltern 70, dolia and urceus type amphorae from Esposende´s Bético Augustano shipwreck. Phase composition was analyzed by XRD which showed the presence of quartz as the main component of all samples. The traces of other crystalline phases were also identified and can be associated to thermal treatment of the ceramic clays. The microstructure of the samples was screened by SEM and the results of EDS confirmed the chemical elements identified by XRD. The principal components analysis indicated chemical composition similarities between amphorae of the same type. The results from the elemental analysis indicated similarities with ceramics characteristic of Guadalquivir valley production centers.
Research Interests:
Resumo: Neste estudo apresenta-se o resultado de análises químicas de resíduos orgânicos efetuados em dois fragmentos de ânfora do naufrágio bético de Esposende, datado do período de Augusto, designadamente um fragmento do bordo de tipo... more
Resumo: Neste estudo apresenta-se o resultado de análises químicas de resíduos orgânicos efetuados em dois fragmentos de ânfora do naufrágio bético de Esposende, datado do período de Augusto, designadamente um fragmento do bordo de tipo urceus (número de inventário PRPESP/05-1/30) e um fundo do tipo Haltern 70 (número de inventário PRPESP/05-1/74). A extração dos resíduos com solventes orgânicos, seguida da análise por cromatografia gasosa com espectrometria de massa acoplada (GC/MS), permitiu a identificação de componentes orgânicos naqueles fragmentos, concluindo-se pela presença de vinho adocicado no fragmento de tipo urceus e de defrutum no fragmento de Haltern 70. Abstract: This study presents results of the chemical analysis of organic residues on two fragments of amphora from the Baetic shipwreck of Esposende, dating from the period of Augustus, including a fragment of an urceus type amphora (inventory number PRPESP/05-1/30) and an Haltern 70 amphora (inventory number PRPESP/05-1/74). The extraction with organic solvents followed by analysis by gas chromatography coupled with mass spectrometry (GC/MS) allowed the identification of organic components, concluding by the presence of sweet wine in the urceus type fragment and by defrutum on the Haltern 70 fragment.
Research Interests:
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The ingestion of licit drugs such as alcohol, tobacco and pharmaceuticals has been rising in Portugal. This trend seems to be related to the period of economic crisis and the increase of unemployment that the country experienced,... more
The ingestion of licit drugs such as alcohol, tobacco and pharmaceuticals has been rising in Portugal. This trend seems to be related to the period of economic crisis and the increase of unemployment that the country experienced, originating an exponential growth in the number of pharmaceutical prescriptions for depression, anxiety and other mental disorders.
Routine clinical exams for the detection of toxic or illicit drugs are usually carried out using blood and urine samples. However, even though they are easy to obtain, blood collection follows invasive procedures while urine has a high risk of adulteration. Moreover, both matrices have a detection window of only a few days for analysis and do not allow distinguishing acute from chronic drug use.
Hair is an alternative biological matrix for toxicological analysis that can also provide a retrospective history of an individual’s drug use. This means that, if a urine specimen is positive for the presence of drugs, hair analysis can discriminate between a single exposure and long-term use. These properties are particularly important in different situations including doping control in athletes, driving license renewal, drug-facilitated crimes, postmortem investigations and/or forensic analysis and therapeutic monitoring.
The patient’s health belief that depression is not a condition needing drug treatment, the lack of knowledge about antidepressants and the fear of side effects during treatment originate frequently poor compliance towards prescribed medication.
In this context, a screening methodology for detection of antidepressants (venlafaxine, fluoxetine and trazodone) in hair was developed based on solid-liquid extraction followed by high performance liquid chromatography with fluorescence detection (HPLC-FLD) or ultra-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). Considering the goals of the study, namely the use of hair analysis for therapeutic monitoring, patients under psychiatric treatments with antidepressants were selected to supply hair samples.
The developed procedure is particularly interesting for routine therapeutic monitoring as it uses relatively inexpensive analytical methodology, simple, sensitive and selective to detect the presence of antidepressants in the patients’ hair. Segmental hair analysis can provide a more accurate record of drug consumption and be used to indicate the history and frequency of drug intake.
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O sangue e a urina são as matrizes biológicas mais frequentemente usadas em exames clínicos para o despiste do consumo de substâncias químicas tóxicas ou ilícitas. Embora seja fácil de obter, a colheita de sangue realiza-se por... more
O sangue e a urina são as matrizes biológicas mais frequentemente usadas em exames clínicos para o despiste do consumo de substâncias químicas tóxicas ou ilícitas. Embora seja fácil de obter, a colheita de sangue realiza-se por procedimentos invasivos enquanto a urina é conhecida como um fluido biológico de alto risco de adulteração. Adicionalmente, estas matrizes permitem apenas obter informações respeitantes a tempos de exposição curtos, de apenas alguns dias.
O cabelo é uma matriz biológica alternativa de recolha simples e não-invasiva, de adulteração praticamente impossível e que permite monitorizar o consumo destas substâncias em períodos de tempo mais ou menos alargados consoante o comprimento do cabelo (1). Esta característica revela-se particularmente importante em situações diversas como a realização de controlos antidopagem em atletas de alta competição, renovação da carta de condução, crimes facilitados devido à presença de drogas, a pesquisa de drogas de abuso, análises toxicológicas pós-morte, e/ou análises forenses (2).
Neste trabalho desenvolveu-se uma metodologia analítica que permite usar o cabelo na monitorização do consumo dos antidepressivos venlafaxina, fluoxetina e trazodona. Genericamente, o procedimento analítico consiste na colheita e homogeneização do cabelo usando um moinho de bolas (3), seguida de extração sólido-líquido (4) e a análise do extrato orgânico por cromatografia líquida com deteção por fluorescência. Atendendo aos objetivos do trabalho selecionaram-se como alvo de estudo pacientes a realizar tratamentos com prescrição de antidepressivos, particularmente aqueles mencionados anteriormente. Os resultados obtidos evidenciaram a presença de fármacos no cabelo destes pacientes, demostrando a metodologia analítica potencialidades para a aplicação em análises de rotina.
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Some Western Europe megaliths are well known for their paintings. Despite their diffusion throughout Europe, they are most common in Northwest Iberia, predominantly in the Galicia and centre-north and north of Portugal. The rock-art... more
Some Western Europe megaliths are well known for their paintings. Despite their diffusion throughout Europe, they are most common in Northwest Iberia, predominantly in the Galicia and centre-north and north of Portugal. The rock-art paintings motifs have been interpreted as part as the funeral practices. However, archaeologists are often unaware on both the colorants composition and the technical solutions used on their production, which, also have a symbolic importance.
In that context, the colorant composition of three northern Portugal megalithic barrows decorated with rock-art motifs (Leandro 5, Maia; Leira das Mamas, Braga and Eireira, Viana do Castelo) was studied using a multi-analytical approach. The use of XRD, SEM-EDS and FTIR combined with GC-MS allowed the characterization of the painting techniques, pigments, and the organic compounds used as binders.

The analytical results obtained allowed the recovery of important data about North-western prehistoric communities, namely the way they exploited existing resources and their ability to transform them.
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Ancient oil lamps made of ceramic were used as a means of artificial lighting or symbolic context, from about 3000 BC until the discovery of electric light in the nineteenth century. This type of lighting, which used animal or vegetable... more
Ancient oil lamps made of ceramic were used as a means of artificial lighting or symbolic context, from about 3000 BC until the discovery of electric light in the nineteenth century. This type of lighting, which used animal or vegetable fats as fuel, accompanied human civilization for millennia and always had a character of the utmost importance, either by its utility or its meaning, as a source of an element essential to human life – light. Three ceramic oil lamps, part of the Egyptian Collection that was donated to the University of Porto, in 1927, by the Berlin State Museums in compensation for the return to Germany of the archaeological collection of artefacts from Mesopotamia that had been seized in Lisbon with the German ship "Cheruskia", at the beginning of First World War. The site where the lamps were found is unknown. It's known that they were acquired in Fayum oasis, at the end of XIX century and, later, by the Neues Museum of Berlim.
When examined under long wave (380 nm) and short wave (254 nm) UV radiation, the “frog-lamp” and one of the D-type (40.01.83) showed fluorescence and phosphorescence in nozzle and inside, a reaction that raised the hypothesis of organic remains existence. This research aims to contribute to its identification. Small samples of inside material were taken by scrapping the surface. Part of the powder collected was subject to Soxhlet extraction with organic solvents and the extracts were analysed by gas chromatography with mass spectrometry (GC-MS). Other part of the powder was subject to scanning electron microscopy and X-ray
microanalysis (SEM-EDS).
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Von flachbodigen Amphoren abgesehen, ist die Individualisierung mancher gebrauchskeramischer Transport- und Vorratsgefäßtypen von besonderem Interesse. Dies gilt beispielweise für die innen mit Harz bestrichenen Krüge und Töpfe. Dieses... more
Von flachbodigen Amphoren abgesehen, ist die Individualisierung
mancher gebrauchskeramischer Transport- und Vorratsgefäßtypen von besonderem Interesse. Dies gilt beispielweise für die innen mit Harz bestrichenen Krüge und Töpfe. Dieses Phänomen, welches nach wie vor einer umfassenderen Bearbeitung bedarf, könnte Hinweise liefern, um die Komplexität antiker andelsbeziehungen neu zu bewerten. Wie der vorliegende Beitrag zeigt, tragen gepinselte Aufschriften (tituli picti) sowie gaschromatografische und massenspektroskopische (GC-MS) Untersuchungen dazu bei, diese Besonderheit besser zu verstehen.
Como parte del estudio de los objetos arqueológicos del sitio arqueológico de El Caño (provincia de Coclé, Panamá), hemos creado una colección de referencia de elementos de la vegetación local que son particularmente prolíficos en... more
Como parte del estudio de los objetos arqueológicos del sitio arqueológico de El Caño (provincia de Coclé, Panamá), hemos creado una colección de referencia de elementos de la vegetación local que son particularmente prolíficos en exudados (resinas y gomas). Estas muestras fueron analizadas por cromatografía de gases en combinación con espectrometría de masas (GC-MS, después de disolución e inyección), y también por la introducción de muestras sólidas seguida de pirólisis analítica (Py-GC-MS y THM-GC-MS). De las 11 muestras de la colección referencia podría ser sencillo distinguir a diferentes niveles de información molecular: i) materiales resinosos vs. gomas, ii) distribución de terpenos (monoterpenos, sesquiterpenos, diterpenos, triterpenos) para resinas o contribuciones de proteínas/taninos/polisacáridos/látex para las gomas; y iii) biomarcadores específicos (estructuras biomoleculares que todavía no han sido identificadas). En el trabajo también se presentan algunos de los resultados obtenidos del análisis de muestras arqueológicas. Una de las figuras de resina parece estar principalmente formada por resinas de las cuales los derivativos de ácido labdánico sugieren de forma sólida que son originarios de resina de Hymenaea. La resina parece estar afectada por fosilización (condensación), lo que implica que estamos ante ámbar. Otras muestras estaban constituidas por ceras y materiales inorgánicos.
Presented in the «Roman Amphora Contents International Interactive Conference (RACIIC) Reflecting on Maritime Trade in foodstuffs in Antiquity», held at Cádiz, Spain in October, 5th – 7th, 2015 (http://amphoraecontentsconference.es/).
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