Nuno Lapa

The objective of this work is to quantify As, Hg, Cd, Ni and Pb in Portuguese red wines. First, the methods for the quantification of trace elements in red wines were validated. Several pre-treatments were compared, namely a pre-digestion process with HNO3, a pre-oxidation step with H2O2, and a spiking step of wine samples with a known concentration of the trace elements analyzed. Except for As, it was determined that the quantification of the trace elements does not require a pre-digestion process with HNO3. For all of the trace elements analyzed, a pre-oxidation step with H2O2 may enable an accurate quantification. The techniques chosen for the quantification of trace elements were hydride generation atomic absorption spectrometry (HGAAS) for As and Hg, electrothermal atomic absorption spectrometry (ETAAS) for Cd, and flame atomic absorption spectrometry (FAAS) for Ni and Pb. In the second stage of this work, 25 Portuguese red wines spanning all of the red wine-producing regions were analyzed for all of the five trace elements referred to above. Only Cd and Pb have shown concentrations above the limit values defined by the “Organization Internationale de la Vigne et du Vin.” The Target Hazard Quotient (THQ) equation was used to determine in which wine-producing regions that wine consumption can be a problem for public health in terms of the concentrations of the five trace elements analyzed. THQ values have indicated that for the universe of the 25 red wines analyzed no region produces wines that can pose problems for public health, when the Portuguese red wine standard consumption is considered.

In 1999, the DEECA/INETI and the UBiA/FCT/UNL started a researching project on the partition of heavy metals during the combustion of stabilised sewage sludge (Biogran®), in a fluidised-bed reactor, and on the quality of the bottom ashes and fly ashes produced. This project was entitled Bimetal and was funded by the Portuguese Foundation for Science and Technology. In this paper only the results on the combustion of Biogran® are reported. The combustion process was performed in two different trials, in which different amounts of sewage sludge and time of combustion were applied. Several ash samples were collected from the bed (bottom ashes) and from two cyclones (first cyclone and second cyclone ashes). Sewage sludge, bed material (sand) and ash samples were submitted to the leaching process defined in the European leaching standard EN 12457-2. The eluates were characterized for a set of inorganic chemical species. The ecotoxicological levels of the eluates were determined for two biological indicators (Vibrio fischeri and Daphnia magna). The results were compared with the limit values of the CEMWE French Regulation. The samples were also ranked according to an index based on the chemical characterization of the eluates. It was observed an increase of the concentration of metals along the combustion system. The ashes trapped in the second cyclone, for both combustion trials, showed the highest concentration of metals in the eluates. Chemically, the ashes of the second cyclone were the most different ones. In the ecotoxicological point of view, the ecotoxicity levels of the eluates of the ashes, for both combustion cycles, did not follow the same pattern as observed for the chemical characterization. The ashes of the first cyclone showed the highest ecotoxicity levels for V. fischeri and D. magna. This difference on chemical and ecotoxicological results proves the need for performing both chemical and ecotoxicological characterizations of the sub-products of such type of thermal processes.

The main aim of the Valomat project was the development of new materials for quarry back-filling and underground constructions, based on the reuse of bottom ashes from MSWI. Bottom ashes were collected in six incineration plants of Europe. Some of them were selected for the development of new materials.
One task of this project comprised the study of the long-term behavior of new materials, under simulated conditions of environmental exposure. Three different scenarios were studied. For each scenario, a pilot plant was constructed and the new materials were studied under laboratory conditions or natural weather. The long-term behavior of these materials was assessed through the characterization of chemical and ecotoxicological properties of the leachates.
The chemical contamination and the ecotoxicological levels of the leachates were relatively low, although different levels had been determined for the three different scenarios. The immersion in dechlorinated tap water (scenario S1) had shown the highest emission levels of chlorides, sulphates, DOC, and Al, especially for the materials B2/1 and B2/2. The lowest ecotoxicological and chemical levels were determined in the scenario in which the materials were buried in a sieved soil.

Portugal has a great diversity of ecoclimatic areas and Sesimbra was chosen to carry out a study on WSP efficiencies over five years (1989 to 1993). According to Pina Manique & Albuquerque (1954), the climate is classified as Atlantic Mediterranean (AM). Some environmental and climatic parameters have been studied in order to define the area. The treatment system at Sesimbra has three ponds: anaerobic, facultative and maturation. The physical and chemical parameters studied in the WSP system were: Temperature, pH, Dissolved Oxygen, Conductivity, BOD5, COD, nitrates, nitrites, ammonia and total nitrogen, total and volatile suspended solids, total phosphorus and orthophosphates. Algal populations and the following microbiological parameters were studied: total and fecal coliforms, fecal Streptococci, Clostridium perfringens, Pseudomonas aeruginosa and some Enterobacteriaceae. The K and K20 kinetic parameters were studied and derived for the three ponds utilizing the seasonal regional characteristics from the surrounding area. These values were then correlated with temperature and the subsequent removal efficiencies for each pond deduced. The data obtained indicate a necessity to determine the seasonal fluctuations of the K and K20 kinetic parameters for the WSP systems.

Plasma is the fourth state of matter, following the three states of solid, liquid and gas. Experience has amply demonstrated that solids exposed to the oxygen-deficient plasma flame are converted to liquid, and liquid exposed to the same flame is converted to gas. A low amount of vitrified solid residue material usually remains at the end of this process. Plasma pyrolysis/vitrification (PP/V) has been demonstrated as a safe, efficient, cost-effective technology for the treatment of wastes, including hazardous wastes. Besides the low amounts of gaseous byproducts that PP/V produces, the solid vitrified residue presents a low leachability of pollutants. Studies have been performed in many countries in order to assess the leachability of chemical substances. But from the results of identified studies, none has reported results on the ecotoxicological properties of the leachates. The aim of this study was to contribute to the assessment of ecotoxic risk of four different vitrified materials. Vitrified samples of contaminated soils, municipal solid wastes, and incinerator bottom ashes were submitted to the European leaching pre-standard test number prEN 12457-2. The leachates were analyzed for 22 chemical parameters. The biological characterization comprised the assessment of bioluminescence inhibition of Photobacterium phosphoreum bacterium, growth inhibition of Pseudokirchneriella subcapitata algae and the germination inhibition of Lactuca sativa vegetable. The chemical and ecotoxicological results were analyzed according to the French proposal of Criteria on the Evaluation Methods of Waste Toxicity (CEMWT) and a Toxicity Classification System (TCS). The chemical and ecotoxicological results indicated a low leachability of pollutants and a low toxicity level of leachates. All samples studied were as below the TCS class 1 level (no significant toxicity observed) and as non-ecotoxic for CEMWT. Therefore, the environmental ecotoxic risk of the analyzed vitrified samples was determined to be very low.

In this paper, chemical and ecotoxicological data of leachates from bottom ashes collected in different Municipal Solid Waste Incinerators (MSWI) are shown. The bottom ashes were collected in Belgium (three incinerators—samples B1 to B3), France, Germany, Italy and United Kingdom (one incinerator in each country—samples F1, D1, I1 and UK1, respectively). Both chemical and ecotoxicological characterizations of leachates were done on the framework of the European Directive 91/689/EEC and the European Council Decision 94/904/EC. This work was carried out under the European project called Valomat, which was supported by the European Commission through Brite-Euram III program. Twenty-one inorganic parameters were analyzed. The ecotoxicological assays were done under standard laboratory conditions, using the bacterium Photobacterium phosphoreum, the freshwater alga Pseudokirchneriella subcapitata, the crustacean Daphnia magna and the vegetable Lactuca sativa. Chemical data varied from sample to sample. Similar results were obtained in biological assays. The samples can be classified as ecotoxic/hazardous according to the French proposal for a Criterion and Evaluation Methods of Waste Ecotoxicity (CEMWE) and the German regulation on Hazardous Waste Classification (HWC). However, samples B1, B2, B3 and D1 comply the maximum limits for direct valorization category defined in the French Classification of Bottom Ashes based on their Polluting Potential (CBAPP). Sample B1 presented the lowest level of ecotoxicity, being considered as the most interesting to be used in the development of new materials for civil engineering works.

Owing to the existing or predictable water deficiencies in the South of Portugal, it is necessary to carry out the appropriate management of water resources, by reducing and/or minimizing the negative impacts of untreated/treated domestic effluents in the aquatic environment. As Portugal has a great diversity of ecoclimatic areas, five different stabilization pond systems were chosen to carry out a control study during one year (from March 1991 to March 1992). According to Pina Manique & Albuquerque the ecological classification of these stations is different, varying from Ibero-mediterranean (continental) up to mediterranean (maritime). The physical and chemical parameters studied were: temperature, pH, dissolved oxygen, conductivity, BOD, COD, nitrates, nitrites, ammonia and total nitrogen, total suspended and volatile solids, total phosphorus and orthophosphates. The microbiological parameters studied were: total and faecal coliforms, faecal Streptococci, Clostridium perfringens and Pseudomonas aeruginosa. The correlations between climatic parameters and the efficiency of the removal of organic matter were analysed.

The analytical values obtained from five WSP systems located in different ecoclimatic zones in the centre and South of Portugal, were subjected to a statistical analysis of K and K20 values (as used in the van Hoff-Arrhenius equation) utilizing an analysis of variance and a vectorial analysis of principal components. Significant differences between K and K20 values in facultative, maturation ponds and in the whole system were verified. The projection of the first principal components of eigenvectors made possible the classification of the stations, showing the existence of similarities and discrepancies in their removal BOD kinetics behaviour. The K20 value must be estimated and taken into account for the design of waste stabilization ponds.

The Water Company of the North Alentejo (Águas do Norte Alentejano) (Portugal) has decided to implement a treatment plant to treat an urban wastewater with a significant influence of tannery effluents. The design of the wastewater treatment plant was attributed to a consortium coordinated by Sisaqua Company. Since the levels of the biodegradability and toxicity of the wastewater to be treated were unknown, Sisaqua Company asked the New University of Lisboa to develop and execute a monitoring plan to define the chemical composition and the levels of the biodegradability and toxicity of the wastewater.
A composite sampling procedure of the wastewater was performed during a daily working cycle of the tanneries. The composite sample was characterized for 19 chemical parameters. Five of these parameters were total Cr, Cr (VI), Zn, Cu and Al, which were determined in the dissolved and suspended fractions. The composite sample was also submitted to a biological test to assess its biodegradability degree. This assay was performed according to the methodology indicated in the test 301E of OECD [1], taking into account the amendment of 1992. A respirometric assay was carried out, to assess the toxic effect of the composite sample on the biological populations involved in the biological stabilization of organic compounds. This assay followed the “Sapromat” methodology developed by Brabander and Vandeputte [2]. Finally, the composite sample was submitted to a coagulation-flocculation process according to the methodologies proposed by Eckenfelder [3, 4] and Pereira [5]. The supernatants were characterized for the same chemical and biological parameters as it was described for the composite sample.
It was possible to conclude that the high levels of Cr present in the composite wastewater were mainly in the trivalent oxidation state. Since this oxidation state is less toxic for biological populations than the Cr (VI) and this metal was mainly in the suspended fraction, it was possible to obtain a biodegradability of the organic compounds quite similar to those observed for domestic wastewaters. The toxicity determined by the “Sapromat” method was slightly higher than those determined for domestic wastewaters. Nevertheless, this toxicity did not affect significantly the wastewater biodegradability. The Cr (III) was easily removed by a chemical coagulation-flocculation process.

This paper is mainly focused on the characterisation of a glass material (GM) obtained from the thermal treatment of a bottom ash (BA) produced at the Municipal Solid Waste (MSW) incineration plant of Valorsul. By melting the BA at 1400ºC during 2 hours, and without using any chemical additives, a homogeneous black-coloured glass was obtained. The thermal and mechanical properties of this glass were characterised. The thermal expansion coefficient, measured by dilatometry, was 9-10 x 10-6 per ºC and the modulus of rupture, determined by four-point bending test, was 75±6 MPa, which are similar values to those exhibited by commercial soda-lime-silica glasses used in structural applications. The chemical and the ecotoxicological leaching behaviour of the GM were also analysed. The GM was submitted to a leaching procedure composed of 15 sequential extraction cycles. A liquid/solid (L/S) ratio of 2 l/kg was applied in each cycle. The leachates were filtered through a membrane of PTFE (porosity: 0.45 µm). The filtered leachates were characterised for different chemical parameters and for an ecotoxicological indicator (bacterium Vibrio fischeri). The GM was also submitted to a microwave acidic digestion for the assessment of the total metal content. The crude BA was also submitted to the same experimental procedures. The GM showed levels of chemical emission and ecotoxicity for V. fischeri much lower than those determined for the crude BA. Similar characterisation studies will be pursued with the glass-ceramics produced by adequate thermal treatment of the glass, in order to investigate the effect of the crystallization on the final properties.

The aim of this study was to evaluate the possibility of the re-use of industrial orange wastes as organic soil fertilizer. The assay was performed with a lettuce variety widely produced and consumed in Portugal and, consequently, with great commercial interest. Lactuca sativa L. (osteolata variety) was cultivated in Mitcherlich pots containing samples of a poor soil of the Algarve region. This soil was prepared with different amounts of either pulp or peel orange-wastes from an orange-juice industry. The wastes were applied according to an increasing amount of nitrogen. The results obtained were submitted to statistical tests, in order to find the relations between the production of fresh and dry matter, and the percentages of nutrients (nitrogen, phosphorous, potassium, calcium, magnesium and iron) that were obtained in the dry matter, with the types and amounts of wastes applied. An increase in the average production of both fresh- and dry-matter with increasing amounts of either pulp or peel wastes applied, and high positive correlation coefficients between the average percentages of nitrogen, phosphorus and potassium obtained in the dry matter with the average production of both fresh- and dry-matter were found. No phytotoxicity was observed.

This work aimed to study the effect of different pre-treatments applied to a potato peel residue, in a thermophilic Anaerobic Digestion (AD) process. All samples were subjected to a mechanical pre-treatment through milling to a particle size below 2 mm. The thermal pre-treatments applied consisted of autoclaving the residue at a gauge pressure of 1.2 bar, under a temperature of 122°C, and for 20, 35 and 55 minutes: assays E122.20, E122.35 and E122.55, respectively. The control assay was performed on a ground residue, which was not submitted to any thermal pre-treatment. All pre-treated residues were subjected to an AD process in a CSTR reactor at 49±1°C. The experimental data showed that the highest methane percentages were very similar (about 92% v/v) for all samples submitted to the thermal pre-treatments. For the control assay, the highest percentage of methane was 87.9% (v/v). The highest biogas yields were recorded in the trial E122.35 (646±50 cm3.g-1 CODremoved), against only 250±20 cm3.g-1 CODremoved for the control assay. The highest biogas yields for VSremoved were attained in the assays E122.55 and E122.35, with values of 646±48 cm3.g-1 VSremoved and 634±59 cm3.g-1 VSremoved, respectively. Globally, the yields registered for the assay E122.35 were similar to those determined in the assay E122.55. Due to the lower energy consumption during the pre-treatment performed in the assay E122.35, this was considered to be the most suitable pre-treatment for this type of residue.