Alberto Coz

Potential influence of CO2 release from a carbon capture storage site on release of trace metals from marine sediment

One of the main risks of CCS (Carbon Capture and Storage) is CO(2) leakage from a storage site. The influence of CO(2) leakage on trace metals leaching from contaminated marine sediment in a potential storage area (Northern Spain) is addressed using standardized leaching tests. The influence of the pH of the leaching solution on the leachates is evaluated using deionized water, natural seawater and acidified seawater at pH = 5, 6 and 7, obtained by CO(2) bubbling. Equilibrium leaching tests (EN 12457) were performed at different liquid-solid ratios and the results of ANC/BNC leaching test (CEN/TS 15364) were modeled using Visual Minteq. Equilibrium tests gave values of the final pH for all seawater leachates between 7 and 8 due to the high acid neutralization capacity of the sediment. Combining leaching test results and geochemical modeling provided insight in the mechanisms and prediction of trace metals leaching in acidified seawater environment.

Biomarker responsiveness in different tissues of caged Ruditapes philippinarum and its use within an integrated sediment quality assessment

Biomarkers comprising activities of biotransformation enzymes (ethoxyresorufin-O-deethylase -EROD-, dibenzylfluorescein dealkylase -DBF-, glutathione S-transferase -GST), antioxidant enzymes (glutathione reductase -GR- and glutathione peroxidase -GPX), lipid peroxidation -LPO- and DNA strand breaks were analyzed in the clam Ruditapes philippinarum caged at Cádiz Bay, Santander Bay and Las Palmas de Gran Canaria (LPGC) Port (Spain). Sediments were characterized. Digestive gland was the most sensitive tissue to sediment contamination. In Cádiz Bay, changes in LPO regarding day 0 were related with metals. In LPGC Port, DBF, EROD, and GST activity responses suggested the presence of undetermined contaminants which might have led to DNA damage. In Santander Bay, PAHs were related with EROD activity, organic and metal contamination was found to be associated with GR and GST activities and DNA damage presented significant (p < 0.05) induction. R. philippinarum was sensitive to sediment contamination at biochemical level. Biomarkers allowed chemical exposure and sediment quality assessment.

Evaluation through column leaching tests of metal release from contaminated estuarine sediment subject to CO2 leakages from Carbon Capture and Storage sites

The pH change and the release of organic matter and metals from sediment, due to the potential CO(2) acidified seawater leakages from a CCS (Carbon Capture and Storage) site are presented. Column leaching test is used to simulate a scenario where a flow of acidified seawater is in contact with recent contaminated sediment. The behavior of pH, dissolved organic carbon (DOC) and metals As, Cd, Cr, Cu, Ni, Pb, Zn, with liquid to solid (L/S) ratio and pH is analyzed. A stepwise strategy using empirical expressions and a geochemical model was conducted to fit experimental release concentrations. Despite the neutralization capacity of the seawater-carbonate rich sediment system, important acidification and releases are expected at local scale at lower pH. The obtained results would be relevant as a line of evidence input of CCS risk assessment, in an International context where strategies to mitigate the climate change would be applied.

Valorization of Foundry Sand in Clay Bricks at Industrial Scale

In this article, foundry sand as waste material has been valorized in ceramic brick manufacturing at industrial scale. The employment of a waste coming from one industry as an input for another is one of the key concepts of industrial ecology. To study the environmental behavior of the ceramic bodies in different life cycle stages, three leaching tests have been developed. We used an EN 12457 equilibrium leaching test with distilled water and a Wastewater Technology Centre acid neutralization capacity (WTC-ANC) leaching test with different acidic leachates to carry out the environmental evaluation under different granular scenarios to ascertain the possibilities of the reuse or disposal of this granular material at the end of its useful life (end-of-life stage). Finally, we used a NEN 7345 diffusion leaching test for construction materials, with the aim of studying the environmental assessment at the use stage. Regulated pollutants in both stages have been evaluated. Furthermore, other soluble salts have been analyzed because they are closely related to the efflorescence phenomenon in bricks. Results indicate that core and green sand from the foundry industry can be used to replace clay content in construction materials, and that these foundry-sand-based ceramics improve some soluble salt results. Despite this fact, at the end-of-life stage in an inert waste landfill, lead, arsenic and chromium can be an environmental problem, both for commercial bricks and for foundry-sand-based bricks. This work can contribute to the determination of viability of sustainable processes of brick manufacturing that use foundry wastes as raw materials.

Physico-chemical and environmental characterisation of sediments from Cantabrian estuaries (Northern Spain)

Previous studies show that sediments of the Cantabrian estuaries (Northern Spain) contain significant concentrations of heavy metals and organic pollutants derived from intensive industrial, agricultural and urban activities. In the most polluted sediments of two estuaries (the bay of Santander and estuary of Suances), physico-chemical and environmental characterisation has been carried out. Water content, density, pH, specific surface, porosity and particle diameter distribution have been evaluated as physical parameters. Total metal contents have been analysed as inorganic parameters. Loss of ignition (LOI), phenol index and extractable organic halogens (EOX) have been determined as organic parameters. Two leachate assays have been carried out in order to evaluate the environmental behaviour of the sediments. Total availability has been analysed using the NEN 7341 test and the mobility of the pollutants has been determined using the EN 12457 leaching test at two liquid/solid ratios. The obtained results have been compared with European Union regulations. The physical parameters and inorganic compounds are very similar in the studied sediments. However, the sediments from Suances have high concentrations of LOI and EOX. The obtained correlation of the physical parameters with the particle size distribution is useful in the study of the sediment addition to ceramic process as a sediment management option. A comparison of the results obtained from the total, availability and mobility analysis of the inorganic pollutant concentrations of As, Ba, Ni, Pb and Zn present in sediments has been made, giving knowledge for the development of regulations and tools that would contribute to the integral management of the estuarine areas.

Study of the delignification of hardwood chips in a pulping process for sugar production

Spent sulphite liquor is a lignocellulosic residue obtained in the acid sulphite pulping process after the digestion of hardwood chips, and composed mainly by lignosulphonates and hemicelluloses. The aim of this work is to study the main process variables at different digestion conditions: maximum temperature, heating rate, and total SO₂ content, which affect the delignification process of hardwood chips to obtain dissolving pulp and to increase the total amount of fermentable sugars and lignosulphonates presented in this lignocellulosic waste. The best results are 210.5 g/L of lignosulphonates and 47.26 g/L of total monosaccharides obtained at higher temperatures of 1.058T and 1.072T, low heating rates of 0.334R and 0.285R, and total SO₂ content of 6.20%. Furthermore, concentrate-acid hydrolysis of the liquor with sulphuric acid was performed in order to study the evolution of the sugar content and the release of the inhibitors. Temperature, acid concentration, acid/liquor ratio and time were modified, showing that acid/liquid ratio is the most influential variable. Although increase in the content of sugars in neither case, a notable furfural and acetic acid concentration decrease is registered, 97.88% and 36.57% respectively, at 20 °C, 60% (w/w) sulphuric acid and acid/sample ratio of 1/0.1 (v/v).

Stabilization/solidification of an alkyd paint waste by carbonation of waste-lime based formulations.

The application of solvent-based paints by spraying in paint booths is extensively used in a wide range of industrial activities for the surface treatment of a vast array of products. The wastes generated as overspray represent an important environmental and managerial problem mainly due to the hazardous characteristics of the organic solvent, rendering it necessary to appropriately manage this waste. In this paper a solidification/stabilization (S/S) process based on accelerated carbonation was investigated as an immobilization pre-treatment prior to the disposal, via landfill, of an alkyd solvent-based paint waste coming from the automotive industry; the purpose of this S/S process was to immobilize the contaminants and reduce their release into the environment. Different formulations of paint waste with lime, lime-coal fly-ash and lime-Portland cement were carbonated to study the effect of the water/solid ratio and carbonation time on the characteristics of the final product. To assess the efficiency of the studied S/S process, metals, anions and dissolved organic carbon (DOC) were analyzed in the leachates obtained from a battery of compliance and characterization leaching tests. Regarding the carbonation of paint waste-lime formulations, a mathematical expression has been proposed to predict the results of the leachability of DOC from carbonated mixtures working at water/solid ratios from 0.2 to 0.6. However, lower DOC concentrations in leachates (400mg/kg DOC in L/S=10 batch leaching test) were obtained when carbonation of paint waste-lime-fly-ash mixtures was used at 10h carbonation and water to solid ratio of 0.2. The flammability characteristics, the total contents of contaminants and the contaminant release rate in compliance leaching tests provide evidence for a final product suitable for deposition in non-hazardous landfills. The characterization of this carbonated sample using a dynamic column leaching test shows a high stabilization of metals, partial immobilization of Cl(-), SO(4)(2-), F(-) and limited retention of DOC. However, the obtained results improve the previous findings obtained after the paint waste S/S using uncarbonated formulations and would be a useful pre-treatment technique of the alkyd paint waste prior to its disposal in a landfill.

Influence of commercial and residual sorbents and silicates as additives on the stabilisation/solidification of organic and inorganic industrial waste.

An environmental problem of the foundry activities is the management of industrial waste generated in different processes. The foundry sludge from gas wet cleaning treatment that contains organic and inorganic compounds and a high content of water is an interesting example. Due to their characteristics, they can be managed using different stabilisation/solidification (S/S) technologies prior to land disposal. The purpose of this work is to study S/S formulations in order to improve the control of the mobility of the pollutants and the ecotoxicity of the samples. Different mixtures of cement or lime as binders and additives (foundry sand, silica fume, sodium silicate, silicic acid, activated carbon and black carbon) have been used in order to reduce the mobility of the chemical and ecotoxicological regulated parameters and to compare the results for commercial and residual additives. The best results have been obtained with sorbents (activated carbon and black carbon) or sodium silicate. The results of the foundry sand ash as additive can conclude that it can be used as replacement in the cement products. However, silica fume in the samples with lime and siliceous resin sand as additives gives products that do not fulfil the regulated limits. Finally, some linear expressions between the chemical parameters and the quantity of material used in the samples have been obtained.

Physico-Chemical Alternatives in Lignocellulosic Materials in Relation to the Kind of Component for Fermenting Purposes

The complete bioconversion of the carbohydrate fraction is of great importance for a lignocellulosic-based biorefinery. However, due to the structure of the lignocellulosic materials, and depending basically on the main parameters within the pretreatment steps, numerous byproducts are generated and they act as inhibitors in the fermentation operations. In this sense, the impact of inhibitory compounds derived from lignocellulosic materials is one of the major challenges for a sustainable biomass-to-biofuel and -bioproduct industry. In order to minimise the negative effects of these compounds, numerous methodologies have been tested including physical, chemical, and biological processes. The main physical and chemical treatments have been studied in this work in relation to the lignocellulosic material and the inhibitor in order to point out the best mechanisms for fermenting purposes. In addition, special attention has been made in the case of lignocellulosic hydrolysates obtained by chemical processes with SO2, due to the complex matrix of these materials and the increase in these methodologies in future biorefinery markets. Recommendations of different detoxification methods have been given.

Monosaccharide production in an acid sulfite process: kinetic modeling.

Spent sulfite liquor is a lignocellulosic waste obtained after the sulfite pulping process. It is mainly formed by sugars and lignosulfonates which are isolated from the pulp during the cooking process. The current work investigates the kinetic modeling of the sulfite process from a biorefinery point of view since monosaccharides present in the spent liquor can be used as a raw material in further biorefinery processes to produce other value-added products. Kinetic parameters of carbohydrate degradation have been determined following sugar and inhibitors from wood to spent liquor, using laboratory scale reactors and different temperatures, 130, 140 and 150 °C. Three types of reaction schemes were developed. Kinetic parameters were obtained for each one using first and n order reactions, using Aspen Custom Modeler. Results show that the best temperature to be used in the process is 130 °C, giving the maximum sugar conversion, 33.91 mol% and obtaining 13.81 mol% of decomposition products.