Critical aspects of biomass ashes utilization in soils: composition, leachability, PAH and PCDD/F

Bottom and fly ashes streams collected along a year in several biomass thermal plants were studied. The bulk composition of ashes and other chemical characteristics that may impact soil application showed a high variability depending on the ash stream, combustion technology and ash management practice at the power plants. The acid neutralization capacity (ANC) and metal’s availability for leaching at fixed pH 7 and 4 was performed according with EA NEN 7371, as a quick evaluation method to provide information on the long-term behavior of ashes, regarding heavy metals and also plant nutrients release. Also the pH dependence leachability study was performed according to CEN/TS 14429 for predicting the leaching behavior under different scenarios. Leachability profiles were established between pH 3 and 12, allowing to distinguish different solubility control phenomena of toxic heavy metals (Cu, Cr, Mn, Ni, Zn, Pb) as well as other salts (Ca, K, Mg, Na, Cl). The ANC of fly ashes at pH 4 (3.6–9.6 molH+/kg) were higher than that observed for the bottom ashes (1.2–2.1 molH+/kg). Ashes were also characterized for persistent organic pollutants (POP), such as polycyclic aromatic hydrocarbons (PAH) and paradibenzodioxines and furanes (PCDD/F). Contents were found to be much higher in fly ash than in bottom ash streams. None of the PAH levels did reach the current national limit value of sewage sludge application in soils or the guide value for ash in north European countries. However, PCDD/F contents, which are not regulated, varied from non-detectable levels to high amounts, regardless the level of loss on ignition (LOI) or unburned carbon content in fly ashes. Given the current ash management practices and possible use of blends of bottom and fly ash streams as soil conditioners resembles clear the urgent need to regulate ash utilization in soils, incorporating limit values both for heavy metals, PAH and PCDD/F

Biomass and coal fly ash as cement replacement on mortar properties

Nowadays, construction sector tries to implement several options to solve the issues related to concrete. The main goal of this work was to study the effect of biomass fly ash, blended with coal fly ashes or alone, as cement replacement in the mortars properties. Mortars with biomass fly ashes have lower slump value than the reference. Mortars with 20% of cement substitution presents better results for all curing time. However, in the three percentages of substitution, and for all curing periods, the best results were found for mortars composed with biomass fly ashes. This work showed that is possible to use biomass fly ashes as partial cement substituent with good results in terms of durability and quality of concrete. Its utilization at an industrial level of concrete production can decrease the energy and raw materials consumption related to cement production and allows a more sustainable option on the ash management.FCT (Fundação para a Ciência e Tecnologia – Portugal) and to the Doctoral Program Eco-Construction and Rehabilitation for supporting the PhD scholarship (with the reference PD/BD/52661/2014

Quantification of GHB and GHB-GLUC in an 1,4-butanediol intoxication: a case report

Gamma-hydroxybutyric acid (GHB) is an endogenous compound with known action at the neural level. Its psychoactive effects led to an illicit use context including recreational purposes, muscle building effects in bodybuilders and drug-facilitated crimes, specifically in sexual assaults. Besides the misuse of the main compound, there are precursors like Gammabutyrolactone (GBL) and 1,4-butanediol (1,4-BD), usually non controlled substances, becoming a much easier way to obtain the target-compound. The authors present the first reported intoxication case in Portugal with 1,4-Butanediol, including the quantification of GHB and GHB-GLUC in serum, by GC-MS/MS TQD. A suspicious liquid and a serum sample were sent by an hospital ER and analysed by GC-MS-single quadrupole and GC-MS/MS TQD, respectively. A methodology including protein precipitation and GC-MS/MS TQD analysis was used to detect and quantify GHB and GHB-GLUC in serum. Toxicological analysis revealed the presence of 1,4-Butanediol in the liquid and GHB [171 mg/L] and GHB-GLUC [13,7 mg/L] in serum. The victim reverted the coma with no neurological sequelae. This was the first detected case, in Portugal, with 1,4-Butanediol, suggesting that it is important to be aware that consumers have different options to obtain illicit compounds, such as GHB. On the other hand, GHB-GLUC was identified and quantified for the first time in a real case, due to intoxication. This case highlights the importance of analysing all samples for active compounds, precursors and metabolites that can lead to the main intoxication origin.publishe

Lime mud from cellulose industry as raw material in cement mortars

This study reports the use of lime mud (LM) in cement-based-mortars. Lime mud is a waste generated in the production of cellulose by the kraft mill process. It is mainly composed of CaCO3, a small amount of magnesium carbonate and other trace minerals. Mortars were prepared by adding different amounts of LM (10, 20 and 30% by weight of cement) in dry weight. The mortar compositions were evaluated through rheology and flow table measurements, assuring that all the samples exhibited adequate conditions for testing in both equipments. The hardened state properties were also evaluated through mechanical strengths at 7, 28 and 90 days of curing. Following a waste management solution perspective, this work intend to provide a general evaluation of LM application in cement based mortars, looking at both fresh and hardened properties in order to guarantee that the final application requirements are not hindered

Prenatal diagnosis of mosaic ring chromosome 16 - a rare event with uncertain prognosis

Ring chromosomes are rare cytogenetic findings (prenatal frequency ~ 0.0075%) often associated with an abnormal phenotype, depending of the chromosomal origin, genetic content and the presence of a mosaic. Supernumerary ring chromosome 16 [r(16)] is rarely observed and mosaicism makes the genotype/phenotype correlation difficult. We report a de novo mosaic r(16) detected after prenatal diagnosis in a woman referred for advanced maternal age. Multiplex ligation-dependent probe amplification (MLPA) for aneuploidy testing of chromosomes 13, 18, 21 and X was normal. Karyotype was 47,XX,+r[10]/46,XX[15]. Chromosomal microarray analysis (CMA) on DNA obtained from long-term cultured amniocytes did not detect any alterations. MLPA with a pericentromeric probe kit on an uncultured sample showed a chromosome 16 gain, encompassing 16p11.2 and 16q11.2 regions, including TGFB1I1, AHSP, VPS35 and ORC6 genes, leading to partial characterization of the r(16). Although no phenotype has been correlated with overexpression of these genes, the 16p11.2 region is associated with neurodevelopmental disorders. Nevertheless individuals with microduplication of 16p11.2 and normal development have been described. The lack of a precise definition of genetic content of the r(16) and its mosaic form leads to uncertain prognosis of clinical outcome.N/

Emission factors from residential combustion appliances burning Portuguese biomass fuels

Smoke from residential wood burning has been identified as a major contributor to air pollution, motivating detailed emission measurements under controlled conditions. A series of experiments were performed to compare the emission levels from two types of wood-stoves to those of fireplaces. Eight types of biomass were burned in the laboratory: wood from seven species of trees grown in the Portuguese forest (Pinus pinaster, Eucalyptus globulus, Quercus suber, Acacia longifolia, Quercus faginea, Olea europaea and Quercus ilex rotundifolia) and briquettes produced from forest biomass waste. Average emission factors were in the ranges 27.5–99.2 g CO kg 1, 552–1660 g CO2 kg 1, 0.66– 1.34 g NO kg 1, and 0.82–4.94 g hydrocarbons kg 1 of biomass burned (dry basis). Average particle emission factors varied between 1.12 and 20.06 g kg 1 biomass burned (dry basis), with higher burn rates producing significantly less particle mass per kg wood burned than the low burn rates. Particle mass emission factors from wood-stoves were lower than those from the fireplace. The average emission factors for organic and elemental carbon were in the intervals 0.24–10.1 and 0.18–0.68 g kg 1 biomass burned (dry basis), respectively. The elemental carbon content of particles emitted from the energyefficient ‘‘chimney type’’ logwood stove was substantially higher than in the conventional cast iron stove and fireplace, whereas the opposite was observed for the organic carbon fraction. Pinus pinaster, the only softwood species among all, was the biofuel with the lowest emissions of particles, CO, NO and hydrocarbons

Ash agglomeration and deposition during combustion of poultry litter in a bubbling fluidized-bed combustor

peer-reviewedn this study, we have characterized the ash resulting from fluidized bed combustion of poultry litter as being dominated by a coarse fraction of crystalline ash composed of alkali-Ca-phosphates and a fine fraction of particulate K2SO4 and KCl. Bed agglomeration was found to be coating-induced with two distinct layers present. The inner layer (0.05–0.09 mm thick) was formed due to the reaction of gaseous potassium with the sand (SiO2) surface forming K-silicates with low melting points. Further chemical reaction on the surface of the bed material strengthened the coating forming a molten glassy phase. The outer layer was composed of loosely bound, fine particulate ash originating from the char. Thermodynamic equilibrium calculations showed slag formation in the combustion zone is highly temperature-dependent, with slag formation predicted to increase from 1.8 kg at 600 °C to 7.35 kg at 1000 °C per hour of operation (5.21 kg of ash). Of this slag phase, SiO2 and K2O were the dominant phases, accounting for almost 95%, highlighting the role of K-silicates in initiating bed agglomeration. The remaining 5% was predicted to consist mainly of Al2O3, K2SO4, and Na2O. Deposition downstream in the low-temperature regions was found to occur mostly through the vaporization–condensation mechanism, with equilibrium decreasing significantly with decreasing temperatures. The dominant alkali chloride-containing gas predicted to form in the combustion zone was KCl, which corresponds with the high KCl content in the fine baghouse ash