Nuno Lapa

The main aim of this work was to assess the possibility of using biomass ashes as substitutes for cement and natural aggregates in concretes without compromising their mechanical and chemical properties. Thirteen concrete formulations were prepared with different percentages of bottom and fly ashes produced at a forest biomass power plant. These formulations were submitted to mechanical compressive strength assays, after 28, 60 and 90 days of maturation. The reference formulation F1 that was produced without biomass ashes and one formulation incorporating fly and bottom ashes, F4, were selected for further characterization. After 90 days of maturation, the selected formulations were submitted to the leaching test described in the European Standard EN12457-2 (L/S ratio of 10 L/kg, in a batch extraction cycle of 24h) by using two different leaching agents: a synthetic marine medium (ASPM medium) and a synthetic freshwater medium (ISO 6341 medium). The eluates produced were submitted to chemical characterization which comprised a set of metals (As, Sb, Se, Cu, Zn, Ba, Hg, Cd, Mo, Pb, Ni, Cr, Cr VI, Al, Fe, Mg, Na, K and Ca), pH, SO42-, F-, dissolved organic carbon, chlorides, phenolic compounds and total dissolved solids. The substitution of 10% cement by fly ashes has not promoted the reduction of the compressive strength of concrete. The new formulation F4 has presented emission levels of chemical species similar or even lower to those observed for the reference formulation F1.

Char residues produced in the co-pyrolysis of different wastes (plastics, pine biomass and used tyres) were characterized using chemical and toxicity assays. One part of the solid chars was submitted to extraction with dichloromethane (DCM) in order to reduce the toxicity of the char residues by removing organic contaminants. The different volatility fractions present in the extracted char (Char A) and in the raw char (Char B) were determined by progressive weight loss combustion. A selected group of heavy metals (Cd, Pb, Zn, Cu, Hg and As) was determined in both chars.

The chars were subjected to the leaching test ISO/TS 21268 – 2, 2007 and the resulting eluates were further characterized by determining a group of inorganic parameters (pH, conductivity, Cd, Pb, Zn, Cu, Hg and As contents) and the concentrations of several organic contaminants (volatile aromatic hydrocarbons and alkyl phenols). An ecotoxicological characterization was also performed by using the bio-indicator Vibrio fischeri.

The chemical and ecotoxicological results were analyzed according to the Council Decision 2003/33/CE and the criteria on the evaluation methods of waste ecotoxicity (CEMWE).

The results obtained in this work indicated that the extraction with DCM is an effective method for the removal of organic contaminants of high to medium volatility from pyrolysis solid residues, thus decreasing their toxicity potential. Zn can be leached from the chars even after the DCM extraction treatment and can contribute to the ecotoxicity of the eluates obtained from chars.

Both chars (treated and non treated with DCM) were classified as hazardous and ecotoxic wastes.

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.

The present work aims to perform a characterization of chars obtained in the co-pyrolysis of waste mixtures composed by plastics, tires and pine biomass, to provide knowledge about the composition, leaching behavior and risk assessment of these materials in order to define strategies for their possible valorization or safe disposal. The chars were submitted to sequential solvent extractions with organic solvents of increasing polarity that allow the recovery of significant amounts of the pyrolysis oils trapped in the crude chars improving the yield of the pyrolysis liquids. An acidic demineralization procedure was successfully applied to the chars and high efficiency removals of the majority of the heavy metals were achieved. The demineralization study also demonstrated that hazardous heavy metals such as chromium, nickel and cadmium are significantly immobilized in the char matrix, and other heavy metals of concern such as zinc and lead will not represent a leaching problem if acidic conditions were not used. The obtained chars present sufficient quality and characteristics to be used as fuel or alternatively, to be used as adsorbents or precursors of activated carbon.

Two combustion tests were performed in a fluidized bed combustor of a thermo-electric power plant: (1) combustion of coal; (2) co-combustion of coal (68.7% w/w), sewage sludge (9.2% w/w) and meat and bone meal (MBM) (22.1% w/w).

Three samples of ashes (bottom, circulating and fly ashes) were collected in each combustion test. The ashes were submitted to the following assays: (a) evaluation of the leaching behaviour; (b) stabilization/solidification of fly ashes and evaluation of the leaching behaviour of the stabilized/solidified (s/s) materials; (c) production of concrete from bottom and circulating ashes. The eluates of all materials were submitted to chemical and ecotoxicological characterizations. The crude ashes have shown similar chemical and ecotoxicological properties. The s/s materials have presented compressive strengths between 25 and 40 MPa, low emission levels of metals through leaching and were classified as non-hazardous materials. The formulations of concrete have presented compressive strengths between 12 and 24 MPa. According to the Dutch Building Materials Decree, some concrete formulations can be used in both scenarios of limited moistening and without insulation, and with permanent moistening and with insulation.

The present work aims to perform a multistep upgrading of chars obtained in the co-pyrolysis of PE, PP and PS plastic wastes, pine biomass and used tires. The quality of the upgraded chars was evaluated by measuring some of their physico-chemical properties in order to assess their valorisation as adsorbents’ precursors. The crude chars were submitted to a sequential solvent extraction with organic solvents of increasing polarity (hexane, mixture 1:1 v/v hexane:acetone and acetone) followed by an acidic demineralization procedure with 1 M HCl solution. The results obtained showed that the upgrading treatment allow the recovery of 63–81% of the pyrolysis oils trapped in the crude chars and a reduction in the char's ash content in the range of 64–86%. The textural and adsorption properties of the upgraded chars were evaluated and the results indicate that the chars are mainly mesoporous and macroporous materials, with adsorption capacities in the range of 3.59–22.2 mg/g for the methylene blue dye. The upgrading treatment allowed to obtain carbonaceous materials with quality to be reused as adsorbents or as precursors for activated carbon.

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 8m). 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.

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 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.

An evaluation of the mycological quality of the sand beaches of the Lisboa and Vale do Tejo coastal area in Portugal was undertaken in May-October 1994. The keratinolytic fungi, yeasts, potential pathogenic and allergic and/or environmental saprophytic fungi were analysed. The results for the yeast Candida were evaluated according to the “Proposed Guidelines for the Microbiological Quality of Sand” (Mendes et al., 1993). The data showed good/satisfactory quality of the sand beaches for the genus Candida. The results indicate that the allergic and/or environmental saprophytic fungi were the most common in sand beaches. The fungi Scopulariopsis and the yeast Candida could be used as specific indicator organisms of sand beaches quality. A new quality objective is introduced that will contribute to improve the sand beaches quality.

Under the framework of the European project named COPOWER, the possibility to partially substitute coal used in a 243 MWth Power Plant by biomass and non-hazardous wastes for the production of electricity and steam was assessed. Three combustion scenarios were studied, based on the combustion tests performed in a Power Plant located in Duisburg (Germany): Scenario 0 (Sc0) – combustion of coal; Scenario 1 (Sc1) – combustion of coal + sewage sludge (SS) + meat and bone meal (MBM); Scenario 2 (Sc2) – coal + SS + wood pellets (WP). An environmental and socio-economic assessment of these three scenarios was performed. In the environmental point of view, Sc0 was the worst scenario, mainly due to the emission of greenhouse gases (GHG). Sc1 was the best scenario, mainly due to the reduction of GHG emission, eutrophication chemical species and ozone depletion gases. In the socio-economic point of view, Sc0 was the worst scenario, mainly due to the absence of GHG abatement, and Sc1 was the best scenario due to the best cost of electricity production and negative cost of avoided emissions.

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.

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.

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.

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.

This paper presents the mobile technology utilization in improving the remote access to the data acquisition processes of several automated monitoring system for air quality, water quality, and crop canopy microclimate. The system facilitates mobile environmental management and decision making by using in-situ measurements, GSM/GPRS informational fluxes, Pocket PCs, dGPS and mobile GIS resources. Data is retrieved via GSM/GPRS data modem to remote computer using digital (GSM) phone network. The main outcomes of this study were as follows: 1. designing the hardware, communication and software infrastructure of the system using telemetry features, 2. establishing the wireless connections and remote access from PDAs to the measurement servers, 3. programming and testing specific control virtual instruments (Vis) in NI LabVIEWTM, 4. obtaining a portable solution of statistical analysis and survey with PDA Vi (Virtual Instruments) interfaces for Pocket PC to gather, store, customize and report data combined with statistical processing functions, and 5. identifying mobile GIS applications for the environmental protection. The remote-accessing of the GIS server features, provided in-situ electronically reviews, mark up, and precise measurements of the site pollution plans. One possible solution to overcome the PDA hardware and software restraints is enabling the remote access and control of the DAQ and GIS software resources of the measurement server via internet.

A method for the determination of 15 aromatic hydrocarbons in eluates from solid residues produced during the co-pyrolysis of plastics and pine biomass was developed. In a first step, several sampling techniques (headspace solid phase microextraction (HS-SPME), static headspace sampling (HS), and dispersive liquid–liquid microextraction (DLLME) were compared in order to evaluate their sensitivity towards these analytes. HS-SPME and HS sampling had the better performance, but DLLME was itself as a technique able to extract volatiles with a significant enrichment factor.

HS sampling coupled with GC–MS was chosen for method validation for the analytes tested. Calibration curves were constructed for each analyte with correlation coefficients higher than 0.999. The limits of detection were in the range of 0.66–37.85 ng/L. The precision of the HS method was evaluated and good repeatability was achieved with relative standard deviations of 4.8–13.2%. The recoveries of the analytes were evaluated by analysing fortified real eluate samples and were in the range of 60.6–113.9%.

The validated method was applied in real eluate samples. Benzene, toluene, ethylbenzene and xylenes (BTEX) were the compounds in higher concentrations.

The DLLME technique coupled with GC–MS was used to investigate the presence of less volatile contaminants in eluate samples. This analysis revealed the presence of significant amounts of alkyl phenols and other aromatic compounds with appreciable water solubility.

Dispersive liquid–liquid microextraction (DLLME) coupled with gas chromatography–mass spectrometry (GC–MS) was applied for the determination of 11 alkylphenols in eluates of chars produced in the co-pyrolysis of different wastes.

The optimized DLLME procedure, 4 mL of sample solution, 15 μL of trichloroethylene as extraction solvent, 1 mL of acetone as dispersion solvent and addition of 15% (w/v) of NaCl, was validated. Under the optimum conditions, the enrichment factors were in the range of 82–180. Calibration curves were constructed for each analyte in pure water in the concentration range of 0.5–8 μg/L with correlation coefficients higher than 0.999. The limits of detection were between 0.07 and 0.17 μg/L. The repeatability of the method was evaluated using water samples fortified with the analyte mixture at two concentration levels: the relative standard deviation (RSD) values were between 3.7% and 8.0% for a concentration of 0.5 μg/L, and between 4.2% and 6.4% for a concentration of 3 μg/L. The recoveries of the analytes evaluated by fortification of real eluate samples were in the range of 67.9–97.9% for eluate 1 (obtained from a decontaminated char) and in the range of 61.9–101.4% for eluate 2 (obtained from the untreated char). o-Methylphenol presented low recoveries for both eluates showing a possible matrix effect. The results obtained show that this method is adequate for the determination of alkylphenols in environmental aqueous samples and presents itself as a fast and inexpensive technique, using minor amounts of organic solvents.

The co-combustion of sewage sludge (SS) and coal is widely used for the treatment and thermal valorization of SS produced in wastewater treatment plants. The chemical and ecotoxicological properties of the ashes produced in this thermal treatment have not been fully studied. Two combustion tests were performed in a fluidized bed combustor. Colombian coal was used as fuel in test A. A blend (1 + 1) of this coal and a stabilized SS (Biogran®) was used in a second test B. Samples of the bottom and fly ashes trapped in two sequential cyclones were collected. The characterization of the ashes was focused on two main aspects: (1) the bulk content of a set of metals and (2) the characterization of eluates produced according to the European Standard leaching test EN 12457-2. The eluates were submitted to an ecotoxicological characterization for two bio-indicators. In what concerns the bulk content of ashes, both combustion tests have produced ashes with different compositions. The ashes formed during the co-combustion test have shown higher concentrations of metals, namely Cr, Cu, Ni, Pb, Zn and Fe for all ashes. The leaching test has shown low mobility of these elements from the by-products produced during the combustion and co-combustion tests. Cr and Cr(VI) were mainly detected in the eluates of the 1st cyclone ashes produced in both combustion tests and in the 2nd cyclone ashes produced in the co-combustion test.

Considering the ecotoxicity assays, the eluates of bottom and fly ashes for both combustion and co-combustion tests have shown low ecotoxic levels. The micro-crustacean Daphnia magna was generally more sensitive than the bacterium Vibrio fischeri. CEMWE criterion has allowed to classify the bottom ashes for both combustion and co-combustion tests as non-toxic residues and the fly ashes collected in both cyclones as toxic.