Armando C. Duarte

Composition of extractable organic matter of air particles from rural and urban Portuguese areas

Abstract Atmospheric particulate matter (PM 10 ) was collected simultaneously at three sites in the West Coast of Portugal, during an intensive campaign in August 1996. The sites were located in line with the breezes blowing from the sea. The collected aerosol was analysed in relation to black and organic carbon content. The particulate organic matter was extracted with solvents and characterised by gas chromatography and mass spectrometry (GC–MS). Most of the organic mass identified consists of alkanes, polycyclic aromatic hydrocarbons (PAH), ketones, aldehydes, alcohols and fatty acids with both biogenic and anthropogenic origin. Many photochemical products from volatile organic compounds emitted by vegetation were also detected. Biomarkers such as 6,10,14-trimethylpentadecanone, abieta-8,11,13-trien-7-one and Patchouli alcohol were observed at higher concentrations in the rural sites. Samples from the urban site present lower values of “carbon preference index” and higher concentrations of petrogenic/pyrogenic species, such as PAH. The PM 10 concentrations and the total organic extract measured for the more interior site were generally lower, indicating that dispersion and dry deposition into the forest canopy were more important during the transport of the air masses than aerosol production by condensation and photochemical reactions. On the contrary, the ratio between organic and black carbon was, in general, lower at sites near the coast, especially for compounds that evaporate at lower temperatures. The organic aerosol composition also seems to be strongly dependent on the meteorology.

Levels, sources and potential human health risks of organic pollutants in urban soils.

Urban soil quality may be severely affected by PAH and PCB contamination, impairing environmental and human health. A comprehensive study was conducted in two contrasting Portuguese urban areas (Lisbon and Viseu) in order to assess the levels of these contaminants and potential risks to human health, to identify sources and study their behavior in soils. The concentrations of PAHs and PCBs were related to the size of the city. The concentrations found in the larger city (Lisbon) were similar to other urban areas. Differences between profiles of the two urban areas were observed for both groups of contaminants, which could be attributed to differences of sources or climate. Lisbon seems to be affected by nearby sources (traffic, industry and incineration processes) whereas in the smaller city atmospheric transport may be playing an important role. Cluster analysis revealed that PAHs and PCBs were associated with anthropogenic toxic elements (Cu, Pb, Zn and Hg in Lisbon; Pb and Hg in Viseu), therefore reflecting common sources. It was also found that organic carbon was an important factor for PAHs and high chlorinated PCB retention in soils. The incremental probability of developing cancer over lifetime, based on a reasonable maximum exposure to PAHs present in Lisbon residential soils, was 9.0 × 10(-6) and 2.4 × 10(-6) for an occupational exposure, both slightly higher than the target risk of 1 × 10(-6). Similarly, the mutagenic risk of PAHs in Lisbon was 3.3 × 10(-5) for residential soils and 1.8 × 10(-6) in recreational areas.

Mercury pollution in Ria de Aveiro (Portugal): a review of the system assessment

The Ria de Aveiro (Portugal) is a coast al lagoon adjacent to the Atlantic Ocean and it has an inner bay (Laranjo bay) that received a highly contaminated effluent discharged by a mercury cell chlor-alkali plant from the 1950s until 1994. The aim of this study is to review in a holistic way several research studies that have been carried out in the Ria de Aveiro, in order to evaluate the remobilization of the mercury accumulated within the system and the recovery of the lagoon. The spatial distribution of the total mercury in the surrounding terrestrial environment has also been considered. Results indicate that the main mercury contamination problems in the Ria de Aveiro are confined to the Laranjo bay. Mercury export to the coastal waters and its impact on the nearshore compartments (water column, sediment and biota) are low. No direct effects of the mercury from nearby industrial activities were detected in Aveiro’s urban soils, although historical mercury contamination is still affecting soil quality in the immediate vicinity of the chlor-alkali plant, located in Estarreja. Moreover, macrophyte harvesting for human direct or indirect use and the consumption of mussels, crabs and the sea bass from the Laranjo bay may constitute a health risk. Further studies focusing on developing skills for the restoration of the ecosystem are presently underway.

Organic components of aerosols in a forested area of central Greece

Total suspended particulate matter was collected in a Abies boressi forest in central Greece during the period of 20 July–12 August 1997. Filters were extracted with solvents and the soluble content was separated into functional group fractions for analyses by gas chromatography/mass spectrometry. A total of 1050 different compounds could be identified in the various extracts. The lipid material consisted primarily of n-alkanes, n-alkan-2-ones, n-alkanols and n-fatty acids, with a higher concentration of molecular weights >C20, derived from vascular plant waxes. Biomarkers for vegetation sources such as phytosterols and triterpenic compounds were also detected. Microbial components (<C20), petroleum residues and pyrogenic aromatic hydrocarbons were present in the various aerosol extracts. Photochemical products deriving from volatile organic compounds emitted by vegetation or from anthropogenic precursors were also detected. These secondary organics include alkane derivatives, di- and carboxylic acids, nitroaromatics and many terpene photo-oxidation products.

Development and application of a capillary electrophoresis based method for the simultaneous screening of six antibiotics in spiked milk samples.

An easy to use and low time consuming capillary electrophoresis (CE) method was developed and applied to the simultaneous determination of six antibiotics (ampicillin, amoxicillin, cloxacillin, penicillin, tetracycline and chloramphenicol) in spiked milk samples. Samples of milk were cleaned up by solid-phase extraction (with a C(18) cartridge) after protein precipitation. Analysis was performed by CE and results compared with the obtained via HPLC, both coupled to a UV-vis detector (210nm). CE employed a 58.5cm long fused-silica capillary (50cm to detector), 75microm i.d., a 2.7x10(-2)M KH(2)PO(4), 4.3x10(-2)M Na(2)B(4)O(7) separation buffer, pH 8; an applied voltage of 18kV; a hydrostatic injection of 0.5psi during 3s; and a run temperature of 25 degrees C. Under the described conditions, amoxicillin was not separated by HPLC, while CE was able to separate, and, therefore, allow detection. Regardless of amoxicillin, comparable results were obtained by HPLC and CE. The average recoveries of antibiotics, from milk fortified at 2.5 and 5microg/mL, was over 72% with R.S.D.s within 5%. Recovery levels were essentially dictated by the used SPE cartridge.

Accumulation of Mercury in Sea Bass from a Contaminated Lagoon (Ria de Aveiro, Portugal)

This work reports the distribution of total mercury (Hg) in Dicentrarchus labrax (sea bass) and in material collected in plankton nets from an inner basin contaminated with the effluent from a chlor-alkali plant, and in other locations of a coastal lagoon (Ria de Aveiro, Portugal). Mercury concentrations were higher in material collected in 200 than in 63 μm mesh net. Mercury in seston decreased pronouncedly with the distance to the industrial source (1.3–0.015 μg g−1 on a wet weight basis), and was higher at low tide than at high tide. This indicates that mercury is exported from the contaminated basin through the first levels of the estuarine chain. Mercury was analysed in muscle, liver, gills and stomach content of sea bass. Specimens captured in the contaminated basin showed higher accumulation of mercury: levels in muscle and liver of young specimens exceeded 1 μg g−1 and 2 μg g−1, respectively; gills and stomach content also presented higher concentrations. Mercury increased more drastically in liver than in muscle of specimens exposed to high contamination, changing the liver/muscle Hg ratio. Although juveniles exhibited higher concentrations in the contaminated basin than in other areas, there is an age effect on the accumulation of mercury in sea bass at the contaminated basin. Occasionally, intermediate concentrations were found in specimens captured in other areas of the lagoon.

(Nano)plastics in the environment - Sources, fates and effects.

Abstract There has been a considerable increase on research of the ecological consequences of microplastics released into the environment, but only a handful of works have focused on the nano-sized particles of polymer-based materials. Though their presence has been difficult to adequately ascertain, due to the inherent technical difficulties for isolating and quantifying them, there is an overall consensus that these are not only present in the environment – either directly released or as the result of weathering of larger fragments – but that they also pose a significant threat to the environment and human health, as well. The reduced size of these particulates ( In this review, we describe the most relevant sources of nanoplastics and offer some insights into their fate once released into the environment. Furthermore, we overview the most prominent effects of these small particulates, while identifying the key challenges scientists currently face in the research of nanoplastics in the environment. Lastly, we give a brief summary of the economic impacts of the pollution caused by plastic litter – a potential key source of nanoplastics – in the oceans, the most common destination of these contaminants.

Nanoscale materials and their use in water contaminants removal—a review

Water scarcity is being recognized as a present and future threat to human activity and as a consequence water purification technologies are gaining major attention worldwide. Nanotechnology has many successful applications in different fields but recently its application for water and wastewater treatment has emerged as a fast-developing, promising area. This review highlights the recent advances on the development of nanoscale materials and processes for treatment of surface water, groundwater and industrial wastewater that are contaminated by toxic metals, organic and inorganic compounds, bacteria and viruses. In addition, the toxic potential of engineered nanomaterials for human health and the environment will also be discussed.

Kinetic approach to heavy metal mobilization assessment in sediments: choose of kinetic equations and models to achieve maximum information.

Studies of trace metal mobilization in sediments are generally performed using sequential extraction schemes at equilibrium. In the present work, a kinetic fractionation of trace metals in sediments has been developed to assess that information. The extraction rate data have been obtained using a single extraction scheme with EDTA and following a protocol previously optimized. Two kinetic equations and two kinetic models were used to fit the experimental data. The two constants equation fits well the extraction rate data used in this work but does not present any physico-chemical meaning. The diffusion model and the two first-order reactions model allow determining which parameter (the reaction between the metal M and the EDTA or the diffusion of the complex M/EDTA) is rate limiting in the trace metal extraction by EDTA. It appears that the two first-order reactions model is more efficient than the diffusion model to fit the present extraction rate data so it can be deduced that the diffusion of the complex M/EDTA is not the limiting step of the trace metal extraction by EDTA in estuarine sediments. In a second part, relationships between the fraction of metals determined with the two first-order reactions model and the sediments composition were established.

Multivariate curve resolution of overlapping voltammetric peaks: quantitative analysis of binary and quaternary metal mixtures

The application of multivariate curve resolution-alternating least squares (MCR-ALS) to the quantitative analysis of different metal ion mixtures using voltammetric data is described. The performance of MCR-ALS was evaluated in the resolution and quantitation of overlapped voltammetric peaks obtained in the analysis of binary and quaternary mixtures of Cd(II), In(III), Pb(II) and Tl(I) metal ions by anodic stripping voltammetry. Quality assessment of qualitative and quantitative determinations was evaluated considering the effects of different constraints and of initial estimations. MCR-ALS results were validated and compared with those obtained by applying other well-established multivariate calibration methods, such as partial least squares (PLS) and direct classical least squares (DCLS) methods.