Granulated biomass fly ash coupled with fenton process for pulp and paper wastewater treatment.

The work describes the combination of granulated biomass fly ash (GBFA) with Fenton process to enhance the removal of adsorbable organic halides (AOX) from pulp bleaching wastewater. At optimal operating conditions, wastewater's chemical and biochemical oxygen demand (COD and BOD5, respectively) and colour were also quantified, and operating cost of treatment assessed. For the first time, raw pulp bleaching wastewater was used to granulate BFA, instead of water, reducing the water footprint of the treatment. Five wastewater treatment setups were studied: (i) conventional Fenton process; (ii) GBFA application; (iii) simultaneous application of GBFA and Fenton process; (iv) sequential treatment by GBFA followed by Fenton process; (v) sequential treatment by Fenton process followed by GBFA. The latter yielded the highest AOX removal (60-70%), whilst COD was also reduced (≈15%) and wastewater biodegradability (BOD5/COD) was enhanced from 0.075 to a maximum of 0.134. Another positive feature of the proposed solution was that GBFA were successfully recovered and reused without regeneration, yielding similar AOX removal compared with fresh GBFA. The operating cost of removing 1 g of AOX from the pulp bleaching wastewater by the optimal treatment setup (60-70% removal of AOX) was 14-26% lower than the operating cost of conducting Fenton process alone (50% removal of AOX).

Valorization of Kraft Pulp and Paper Mill Slaker Grits and Biomass Fly Ash as Fillers in a Commercial Screed Mortar Formulation.

Slaker grits (SG) and biomass fly ash (BFA), two waste streams generated in the pulp and paper industry, are commonly disposed of in landfills, a practice with a high economic and environmental burden. In this work, their individual valorization as fillers in a commercial screed mortar formulation was evaluated in order to achieve a more sustainable management practice. The waste streams were characterized in terms of true density, particle size and morphology, and chemical and mineralogical composition. The influence of their incorporation amount (5.0, 7.5, and 10.0 wt.% of the total solids) and pre-treatment (sieving and grinding) on the fresh (workability) and hardened state (density, water absorption by capillarity, and flexural and compressive strength) properties of the mortars were assessed. The results show that the addition of 10.0 wt.% of the SG after milling and sieving (<75 µm) and 7.5 wt.% of BFA in the as-received condition, or up to 10.0 wt.% after grinding and sieving (<63 µm), allowed for the production of mortar samples with properties within the recommended specifications and that were resistant to 25 consecutive freeze-thaw cycles. This waste valorization route could represent an economic benefit of up to 8.85 €/tmortar and 2.87 €/tmortar for mortar, and pulp and paper companies, respectively.

Conversion of quinoa and lupin agro-residues into biochar in the Andes: An experimental study in a pilot-scale auger-type reactor.

In the last decades, the cultivation of quinoa and lupin became an important source of income for Andean farmers due to the demand for high nutrient-density foods from the Global North. The increase in the cultivation intensity caused by this exogenous demand led to the overexploitation of local ecosystems and a decrease in soil fertility. As an alternative to recover and improve soil quality, this work uses a pilot-scale auger pyrolysis reactor, implemented in the Andes, to assess the conversion of the agro residues generated in the post-harvesting processes of quinoa and lupin into biochar for soil amendment. Following the European Biochar Certificate guidelines, the pyrolyzed quinoa stems can be classified as biochar while the pyrolyzed quinoa husks can be classified as pyrogenic carbonaceous material. Both can be used for soil amendment considering their molar ratios (H/Corg, O/Corg) and carbon content. It was not possible to carbonize lupin stems and seedcases. Despite the altitude (2,632 m.a.s.l), the CO concentration during the carbonization of quinoa stems and husks were 1,024.4 and 559 mg/Nm3, this last, near the European eco-design standard of 500 mg/Nm3. A subsequent SWOT analysis showed the need to explore low-cost and low-complexity pyrolysis reactors that allow the decentralized conversion of agro residues at the farm-scale. The development of local standards to regulate the production and use of biochar is also essential to grant the safety of the processes, the quality of the products, and mobilize funds that allow implementation at relevant scales.

Biomass ash formulations as sustainable improvers for mining soil health recovery: Linking soil properties and ecotoxicity.

There is a growing need to recover degraded soils to restore their essential ecosystem services and limit damages of anthropic activities onto these systems. Safe and sustainable solutions for long-term recovery must be designed, ideally by recycling existing resources. Using ash from combustion of residual forest biomass at the pulp and paper industry is an interesting and sustainable strategy to recover mining soils. However, formulations must be found to limit the potential toxicity associated with soluble salts and chloride that ash contains. Here, we assessed the effectiveness of three field ash-based amendments for the recovery of three highly acidic soils from Portuguese abandoned mines. Three amendments were tested: an un-stabilized mixture of ash and biological sludge, granulated ash, and granulated ash mixed with composted sludge. One year after application in open field plots (in the scope of LIFE No_Waste project), soil health restoration was evaluated through (i) soil physico-chemical characterization and (ii) soil habitat functions though standardized ecotoxicological tests. This study highlights that stabilized materials provided nutrients, organic matter and alkalinity that corrected soil pH and decreased metal bioavailability, while controlling the release of soluble salts and chloride from ash. This soil improvement correlated with improved soil model organisms' reproduction and survival. For similar amendment, the native soil properties studied (as soil native electrical conductivity) affected the level of organism response. This work provides evidence that ash stabilization, formulation and supplementation with organic matter could be sustainable strategies to restore highly degraded mining soils and to recover their ecological functions. It further highlights the importance of analyzing combined effects on soil physico-chemical properties and ecological function recovery to assess restoration strategy efficiencies in complex multi-stressor environments.

Role of waste-based geopolymer spheres addition for pH control and efficiency enhancement of anaerobic digestion process.

In anaerobic digestion processes, pH has a vital role due to the direct impacts on the microbial community. An eco-friendly approach has been applied to control pH in anaerobic bioreactors, using waste-containing fly ash geopolymer spheres (GS) instead of powdered chemical compounds, to promote continuous alkalis leaching. The influence of GS porosity and concentration on the behavior of anaerobic sequential batch reactor treating cheese whey was evaluated. Results showed that the use of GS with the highest concentration and porosity promoted an increase in methane yield up to 30%, compared to the assay with powdered chemical compounds addition. In addition, GS boosted butyric acid production to the detriment of propionic acid, which favored methane production by a factor up to 1.2. This innovative approach indicates that GS addition can regulate pH in anaerobic digesters treating challenging wastewaters and, simultaneously, improve not only its efficiency but also the sustainability of the entire process.

Life cycle assessment of woody biomass ash for soil amelioration.

The increasing use of forest biomass as a fuel for power plants due to environmental concerns will certainly increase the amount of woody biomass ash produced. Because of the environmental problems derived from woody biomass ash disposal, an important aspect for the sustainable development of the energy sector is the implementation of effective ash management strategies. The purpose of this study is to assess the environmental impacts of woody biomass ash landfarming for soil amelioration through a Life Cycle Assessment. The baseline scenario corresponds to the current most common practice of woody biomass ash management (landfilling), and two different landfarming alternatives were assessed: liming and fertilisation. Credits were given to the system due to the substitution of three traditional liming products and five traditional fertilisers. Woody biomass ash landfarming presented satisfactory performance in five impact categories under study in comparison to landfilling. When woody biomass ash was used for liming, the environmental savings were more pronounced when substituting hydrated lime. For potassium supply, the substitution of potassium nitrate by woody biomass ash presented the best environmental performance, while for phosphorus supply, the environmental savings were more pronounced substituting single superphosphate. However, in four impact categories, the environmental impacts of ash landfarming exceeded the impacts of ash landfilling, due to the emission to soil of nutrients and trace elements to soil. But this does not necessarily imply increased risks for the environment, as the potential pollutants leaching depends on their bioavailability in the soil.

Use of wastes from the pulp and paper industry for the remediation of soils degraded by mining activities: Chemical, biochemical and ecotoxicological effects.

Fly ash (FA) from biomass combustion and biological sludge (S), both wastes from the pulp and paper industry, were granulated in different proportions (90% FA+10% S, and 70% FA+30% S w/w, dry weight basis, dw) and used to recover the functionality of soils affected by mining activities (Aljustrel, Iberian Pyrite Belt), with and without the application of municipal solid waste compost (MSWC). Application doses of both mixtures were 2.5, 5.0 and 10% (w/w, dw). These materials corrected soil acidity to circumneutral values and increased extractable P and K concentrations. A significant increase in soil organic matter (from 0.6 to 0.8-1.5% w/w, dw) and N content (from 0.04 to 0.09-0.12% w/w, dw) was also observed, but only when MSWC was applied. The soil was already heavily contaminated with Cu, Pb and Zn and the application of amendments did not increase their pseudo-total concentrations. The CaCl2 extractable fractions of both Cu and Zn decreased to very low values. The improvement in soil quality, compared to fertilizer only treatment, was further evidenced by the increase in some soil enzymatic activities (dehydrogenase, ß-glucosidase and cellulase), with a better response for the granules with the higher proportion of biological sludge, as well as by the decrease in the soil-water extract toxicity towards different organisms (Daphnia magna, Thamnocephalus platyurus, and Pseudokirchneriella subcapitata). Agrostis tenuis germinated and grew during the first month only in the amended pots, but, after that, a considerable phytotoxic effect was evident. This was mainly attributed to salt stress or to some specific ionic toxicity. In conclusion, to establish a long-term plant cover in mining soils amended with biomass ash-based materials, the selection of plants with higher resistance to salinity and/or the stabilization of the amendments, to reduce their soluble salt content, is recommended.

Mineralogical, chemical and leaching characteristics of ashes from residential biomass combustion.

Four types of pellets and three agro-fuels were chemically characterised and burned in a pellet stove. To assess the influence of the material composing the firebox and the combustion efficiency of distinct biomass heating devices in the composition of the bottom ashes, three of the pellets were also burned in a conventional woodstove and in a fireplace. Ashes were analysed for their C, H and N contents by an elemental analyser, whilst major and trace elements were quantified by inductively coupled plasma atomic-emission spectrometry and inductively coupled plasma mass spectrometry, respectively. The mineralogy of ashes was determined by X-ray powder diffraction. The European standard test was applied to samples to determine the leaching potential of major, minor and trace elements. The contents of major and trace elements in the different types of biomass presented enormous variations, which are reflected in dissimilar mineralogical and chemical compositions of the respective ashes. The leachable potential of several elements of environmental concern present in oxy-anionic form at the alkaline pH of biomass ashes were generally high in all samples. Concentrations of some elements in the leachates were in the range of values with classification of "hazardous materials" by the European legislation in what respects the acceptance of these wastes at landfills. Pellets made up of wood wastes and containing preservatives (chromated copper arsenate and ammoniacal copper arsenate) are of concern. Due to lower combustion efficiencies, the leachable potential for most of the trace elements in ashes from the woodstove, and especially from the fireplace, was lower than that of the pellet stove.

Effect of industrial and domestic ash from biomass combustion, and spent coffee grounds, on soil fertility and plant growth: experiments at field conditions.

An experimental study was conducted at field conditions in order to evaluate the effect of application of ash from biomass combustion on some soil fertility characteristics and plant growth. Application of 7.5 Mg ha-1 industrial fly ash (IA), domestic ash (DA), and a 50:50 mix of domestic ash (DA) and spent coffee grounds (SCG) was made in different soil parcels. Lolium perenne seeds were sown and the grown biomass was harvested and quantified after 60 days. Soil samples from each parcel were also collected after that period and characterized. Both soil and grown biomass samples were analyzed for Ca, Mg, Na, K, P, Fe, Mn, Zn, and Al contents. Soil pH was determined before and after amendment. All applications rose significantly soil pH. Domestic ash, whether combined with coffee grounds or not, proved to be efficient at supplying available macronutrients Ca, Mg, K, and P to the soil and also reducing availability of Al (more than industrial ash). However, it inhibited plant growth, even more when combined with spent coffee grounds. As regards to elemental abundance in plant tissue, both domestic ash treatments reduced Ca and enhanced Al contents, unlike industrial ash, which proved less harmful for the load applied in the soil. Hence, it was possible to conclude that application load should be a limiting factor for this management option for the studied materials.

Ashes from fluidized bed combustion of residual forest biomass: recycling to soil as a viable management option.

Although bottom ash (BA) [or mixtures of bottom and fly ash (FA)] from clean biomass fuels is currently used as liming agent, additive for compost, and fertilizer on agricultural and forest soils in certain European countries, in several other countries most of the ashes are currently disposed in landfills. This is due to both a lack of a proper classification of the materials and of regulatory barriers.Chemical characterization including analysis of an array of potentially toxic elements (PTEs) proved that over 100,000 tons of BA currently landfilled every year in Portugal actually complied with legal limits for PTEs for soil fertilizers applied in other countries. Pot experiments were conducted, testing three dosages of BA and FA (1, 2.5, and 5%, in weight) in three mining soils with different properties. Additions of ash materials to soils led to an increase in the pore water pH relative to control pots (0% of ash added) and had a clear impact on DOC and on the solubilization of both macro- and micronutrients (notably Cu).The results from the case study using BA and FA from a Portuguese biomass thermal power plant demonstrate that it is imperative to further develop a regulatory framework to alleviate technological and environmental barriers for biomass ash utilization as raw material for fertilizers and/or soil liming agent, in accordance with the goals of the circular economy. A more harmonized view on how to assess the merits and risks of the re-use of these materials is also needed.

Characteristics of ash and particle emissions during bubbling fluidised bed combustion of three types of residual forest biomass.

Combustion of residual forest biomass (RFB) derived from eucalypt (Eucalyptus globulus), pine (Pinus pinaster) and golden wattle (Acacia longifolia) was evaluated in a pilot-scale bubbling fluidised bed reactor (BFBR). During the combustion experiments, monitoring of temperature, pressure and exhaust gas composition has been made. Ash samples were collected at several locations along the furnace and flue gas treatment devices (cyclone and bag filter) after each combustion experiment and were analysed for their unburnt carbon content and chemical composition. Total suspended particles (TSP) in the combustion flue gas were evaluated at the inlet and outlet of cyclone and baghouse filter and further analysed for organic and elemental carbon, carbonates and 57 chemical elements. High particulate matter collection efficiencies in the range of 94-99% were observed for the baghouse, while removal rates of only 1.4-17% were registered for the cyclone. Due to the sand bed, Si was the major element in bottom ashes. Fly ashes, in particular those from eucalypt combustion, were especially rich in CaO, followed by relevant amounts of SiO2, MgO and K2O. Ash characteristics varied among experiments, showing that their inorganic composition strongly depends on both the biomass composition and combustion conditions. Inorganic constituents accounted for TSP mass fractions up to 40 wt%. Elemental carbon, organic matter and carbonates contributed to TSP mass fractions in the ranges 0.58-44%, 0.79-78% and 0.01-1.7%, respectively.

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.

Characterisation and use of biomass fly ash in cement-based materials.

This paper presents results about the characterisation of the biomass fly ashes sourced from a thermal power plant and from a co-generation power plant located in Portugal, and the study of new cement formulations incorporated with the biomass fly ashes. The study includes a comparative analysis of the phase formation, setting and mechanical behaviour of the new cement-fly ash formulations based on these biomass fly ashes. Techniques such as X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), thermal gravimetric and differential thermal analysis (TG/DTA), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and environmental scanning electron spectroscopy (ESEM) were used to determine the structure and composition of the formulations. Fly ash F1 from the thermal power plant contained levels of SiO(2), Al(2)O(3) and Fe(2)O(3) indicating the possibility of exhibiting pozzolanic properties. Fly ash F2 from the co-generation plant contained a higher quantity of CaO ( approximately 25%). The fly ashes are similar to class C fly ashes according to EN 450 on the basis of chemical composition. The hydration rate and phase formation are greatly dependant on the samples' alkali content and water to binder (w/b) ratio. In cement based mortar with 10% fly ash the basic strength was maintained, however, when 20% fly ash was added the mechanical strength was around 75% of the reference cement mortar. The fly ashes contained significant levels of chloride and sulphate and it is suggested that the performance of fly ash-cement binders could be improved by the removal or control of these chemical species.