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Sewage sludge (SS) formed in wastewater treatment plants can contain organic matter and nutrients in concentrations that are valuable for amending poor soil. This work aims to compare the performance of six residues not only as drying adjuvants of SS but also as improvers agents in agronomic properties of the final product. According to criteria in line with circular economy and industrial ecology, the selected adjuvants were weathered coal fly ash (CFA), bottom biomass ash (BBA), green liquor dregs (GLD), lime mud (LM), eggshell (ES), and rice husk (RH). The main physicochemical properties of these materials were determined. Then, small cylinders with and without 0.15 g adjuvant/g SSwet basis were shaped at room temperature and dried at 130 oC in a moisture analyzer to evaluate the drying kinetics. The profiles were modeled, and the main parameters determined. Furthermore, several relevant parameters for agronomic applications of the final products were determined, such as pathogen contamination, acid neutralization capacity (ANC), and oxygen uptake rate (OUR). Adding BBA to SS (named as SS_BBA product) promoted the highest diffusion coefficient (2.55·10−7 m2/s) and drying rate (41.6 g H2O/kg min). On the other hand, SS_ES showed a positive impact in almost all agronomic parameters, with an ANC of 0.166 g CaCO3/g, OUR of 10.18 mmol O2/kg organic matter h, and germination index of 29.1%. In general, the results indicate that several residues can be used to improve not only sludge drying but also the final properties of the product for soil applications.

This work presents an updated overview of waste lubricant oil (WLO) management practices in Europe to promote a circular economy. The characteristics of virgin and waste oil, their hazardous proper...

The biorefinery approach must be boosted in the management of agro-residues in the future. The present study aims to investigate the valorization of tomato production residues, namely rotten tomato (unfit for consumption - RT), green tomato (GT), and tomato branches (TB). The assessment involves the recovery of value-added compounds through the extraction process followed by biogas production through anaerobic digestion. A thorough characterization of the three residues (RT, GT, and TB) was carried out, including the identification of volatile compounds by solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS). The volatiles analysis revealed the presence of flavor enhancer compounds and molecules with insecticidal properties. A solid-liquid extraction with ethanol allowed the recovery of value-added compounds in the extracts, in particular phenolic compounds, β-carotene, and lycopene, which contributed to the antioxidant activity. RT and TB extracts were found to be richer in total phenolic compounds (~27 mg GAE/gdb dry basis) and exhibited higher antioxidant activity (IC50 = 0.911 and 0.745 mg/mL). The tomato branches extract had the highest concentration of carotenoids with 37.23 and 3.08 mg/kgdb of β-carotene and lycopene, respectively. The biochemical methane potential (BMP) was assessed in sealed reactors operating in anaerobic conditions for all the raw (RT, GT, and TB) and extracted substrates waste (RTe, GTe, and TBe). While the BMP of RT and GT was in the range of 232–285 mL CH4/g VS, a lower value of 141 mL CH4/g VS was obtained for TB. The methane production for each pair of raw and extracted substrates (RT/RTe, GT/GTe, and TB/TBe) was considered statistically similar at a 95 % confidence level. Overall, the value-added compounds recovery through ethanolic extraction did not compromise the methane production of the materials.

Sewage sludge (SS) is a global environmental, social, and economic problem that requires a sustainable management approach. Still, the production of other industrial wastes, such as lime mud (LM), has recently gained considerable attention to avoid landfilling. This work aims to present a new approach for converting SS and LM into value-added products within the circular economy perspective. In particular, the effect of LM and calcined lime mud (CLM) as drying adjuvants and SS sanitation agents are investigated. Two out of three SS samples show Escherichia coli contamination above the Portuguese limit established for soil application, while no Salmonella spp. was detected in the searched samples. The addition of CLM to SS in a ratio between 0.05 and 0.15 g CLM/gwb, lead to complete elimination of the microbiological contamination in almost all cases. Contrarily, the use of LM does not seem efficient to act as a sanitation agent. Both LM and CLM show a positive impact on the drying process when compared to the raw SS, increasing the drying rate, and reducing the drying time. The most favourable drying conditions to maximize the drying rate and minimize the drying time (until 30% of moisture) are 130 °C, 0.15 g adj/gwb, and 2.5 mm of plate thickness. The thermal treatment (100 and 130 °C) without adjuvants reduces the microbiological contamination below the legal limit. Overall, a beneficial effect is observed by adding CLM to SS, open the possibility of producing a safer organic soil improver.

Phosphorus (P) is a non-renewable resource, irreplaceable for life and food production, and currently considered a Critical Raw Material to the European Union (EU). Due to concerns about the rate of consumption and limited reserves in countries with sensitive geopolitical contexts, it is urgent to recover P from urban and industrial flows. Indeed, the municipal wastewater treatment plants (WWTP) are considered relevant sources with several hot spots, especially sewage sludge with estimated recovery efficiencies of >80%. The most promising recovery strategies are based on thermal treatments (e.g., incineration of sludge) following by wet-chemical or thermochemical leaching, precipitation, and adsorption. The direct application of sludge on soil is no longer a primary route for P reintegration in the value-chain for countries as Switzerland, Germany, and The Netherlands. In fact, Switzerland and Austria paved the way for implementing P recovery legislation, focusing on recovery from raw sewage sludge or ashes. Indeed, industrial technologies with sludge ash as input show high recovery efficiencies (Ashdec® and Leachphos® with 98 and 79%) and lower environmental impacts, whereas Pearl® technology has about 12% recovery efficiency with wastewater as input. After all, struvite emerges as the most recovered product with recent access to the internal market of EU fertilisers and similar growth performance compared to triple-super-phosphate. However, several studies leave open the possibility of introducing loaded adsorbents with P as soil amendments as a new alternative to conventional desorption. Briefly, P recovery should be a compromise between efficiency, environmental impacts, and economic revenues from the final products info:eu-repo/semantics/publishedVersion

In this study, the performance of chemically modified pine bark for removal of Cr(III) from solutions was investigated. Initially, several chemicals were tested (NaOH, C5H9NO4, H3PO2 and CS2). The xanthate pine bark (XPB) obtained with CS2, was screened as the best adsorbent and thus, it was characterized in respect to morphological and textural properties. Sulfur groups after xanthation reaction were identified on XPB by FTIR and EDS spectroscopies. Equilibrium isotherm and kinetics were determined. The equilibrium data were well described by the Langmuir isotherm allowing to calculate the maximum adsorption capacity (56.5 mg/g). The kinetics is fast and follows a pseudo-second order model. Furthermore, an ion-exchange sorption mechanism between Cr(III) and Na+ was proposed. Among the desorbing agents tested, the best results were achieved with 2.0 M H2SO4. Moreover, in the column tests, a reduction on the breakthrough time and the stoichiometric time from 36.5 and 22.8%, respectively, was observed, when the feed concentration increased from 230 to 500 mg/L. The breakthrough curves were well modeled by Bohard-Adams, Thomas or Yoon-Nelson equations. Globally, XPB revealed to be a promising adsorbent for uptake Cr(III). The scale-up design and the economic assessment indicated potential applicability for the treatment of real effluents.

Coagulation phenomena can occur in certain types of waste lubricant oils (WLO) during regeneration processes involving alkaline treatments, causing plant shutdowns. In this context, this study addresses the nature of the compounds responsible for the coagulation phenomena after the alkaline treatment. For such, an empirical test was developed to assess the coagulation behaviour of WLO, consisting in the addition of KOH to the WLO followed by heating under stirring conditions. This test was performed on 133 samples and four coagulation classes were identified: A; B1; B2 and C. Moreover, a physicochemical characterization of WLO was carried out regarding viscosity at 40°C, saponification number (SN), total acid number (TAN), surface tension, water content, elemental analysis and functional groups (FTIR). 56 samples of fresh lubricant oils for different applications were also characterized and their properties assessed and compared. Multivariate methods were applied to WLO to discriminate among coagulation classes based on FTIR spectra. It was found that coagulation classes A and B1 exhibit statistically similar patterns for all properties determined. Spectral discriminating analysis did not reveal discriminant peaks for class B1 samples, and the presence of specific additives was pointed as the possible factor underlying the increase in viscosity in this oils. Class B2 presents the absence of additives and oxidation products as differentiating features. In addition, B2 samples showed lower TAN SN, and lower concentration of some elements. Lubricants from gear or hydraulic applications can give rise to this class of WLO. Oils of Class C are mainly composed by synthetic ester type base oils, which hamper regeneration processes using alkaline pretreatments. In future studies, WLO type A and B1 can be classified as a single class. The coagulation phenomena classification becomes A - negative, B - precipitate formation and C - positive.

The main objective of this work is to evaluate the phytotoxicity of olive mill solid wastes (OMW) produced in two different centrifugation technologies and also the toxicity associated with specific phenolic compounds. Two samples of waste were collected in two-phase (2P-OMW) and three-phase (3P-OMW) centrifugation olive oil production processes, and cress bioassays with Lepidium sativum L. were employed to evaluate phytotoxicity. Although both OMW have similar total phenolic content (TPh), results confirmed that 2P-OMW is more phytotoxic than 3P-OMW. When extracts from 2P-OMW at liquid to solid ratio of 10 L kg−1 were applied none of the seeds germinated, i.e. germination index ( G I ) was 0%, while for 3P-OMW GI was 94.3%. Growth tests in soil and mixtures with OMW also led to more favorable results for 3P-OMW, whereas worse results than those obtained in the control experiments were observed. In order to discriminate the individual influence of eleven phenolic compounds, gallic acid, protocatechuic acid, cinnamic acid, syringic acid, 3,4,5-trimethoxybenzoic acid, 4-hydroxybenzoic acid, vanillic acid, p-coumaric acid, caffeic acid, veratric acid and phenol were tested in the concentration range of 5–500 mg L−1. Results showed that cinnamic acid is the most phytotoxic, with EC50 of 60 mg L−1, which is related with its hydrophobicity. Moreover, increasing -OH and -OCH3 groups in these molecules seem to reduce phytotoxicity. Tests with a mixture of six phenolic compounds demonstrated there are neither synergistic nor additive effects. The phytotoxicity appears to be determined by the presence of the most lipophilic phenolic molecule.

Nowadays the European guidelines boost the concept of “circular economy” which is focused on catalysing sustainable development. “Closing the loop” is particularly important for improving the recycling rates, and thus waste and by-products can be turned into a resource with benefits to the economy and environment. Within this scope, this work reviews and updates the potential of valorisation and legal framework of an anthropogenic biomineral with high content of calcium carbonate. Namely, the waste under consideration is the industrial eggshell waste (ES) resulting from egg breakage. This is considered an animal by-product (ABP) and thus some constraints may limit ES applications. The flux of this ABP mainly within the European region is also indicated and the estimated data highlight that significant amount of this biomineral is being produced. Despite legal restrictions, countries such as the UK, Spain and Portugal have been able to find practical application for ES, avoiding landfilling. The literature shows that applications for industrial eggshell may be grouped into two categories: raw material and operating supply. In the first case, the options are food additive, soil amendment, purified calcium carbonate, cosmetics and biomaterial composite. As operating supply, ES may be used as catalyst and sorbent. Although the economic profit should be evaluated in each case, the environmental benefit of those potential applications is in general high. Considering ES properties and the soil properties in large areas of Europe (acidic pH and low topsoil organic carbon content) the production of Ca-rich compost obtained through composting seems to be a particularly interesting approach toward “circular economy”.

Compost from poultry hatchery waste (CPHW) was used as an efficient biosorbent for the removal of heavy metals from aqueous solutions. Single and competitive adsorption of Cd(II) and Pb(II) onto CPHW were studied. The optimum pH of the aqueous solution for Cd(II) and Pb(II) adsorption was found to be in the range 3 to 5. The pseudo-second order model enabled a better description of the adsorption kinetics. Equilibrium data obtained at 25, 35, and 45 °C were better described by the Sips isotherm than by the Freundlich and Langmuir models. The maximum adsorption capacities calculated by applying the Sips isotherm were 32.3 mg/g for Cd(II) and 142.6 mg/g for Pb(II) at 25 °C. In binary metal ion solutions, a decrease in the adsorption capacity for both heavy metals was observed. The single and competitive adsorption tests revealed that the adsorption affinity was higher for Pb(II) than for Cd(II). Thermodynamic parameters such as ΔG0, ΔH0, and ΔS0 indicated that the adsorption was feasible, spontaneous, and endothermic. FTIR spectroscopy characterization showed that carboxyl and hydroxyl groups were involved in the adsorption of the metals. SEM-EDX analysis confirmed that Cd(II) and Pb(II) may replace Ca(II) from biosorbent surface. Therefore, the results suggest that CPHW can be used as an economical biosorbent for Pb(II) and Cd(II) removal from aqueous solutions.

This study aims to investigate the sewage sludge (SS) drying process by incorporating a by-product formed in the pulp and paper industry (green liquor dregs - GLD) as drying adjuvant. Through an innovative approach, the drying kinetics was modelled, and the final dried product was tested for soil applications. After the characterization phase, small cylinders of SS without and with 0.15 g GLD g SS−1wb (SS_GLD) were dried in isothermal conditions at 70, 100, and 130 °C. The experimental data were fitted by Fick's second law and thin-layer models, and good results were achieved in both cases (R2 > 0.98 and RMSE

Phosphorus scarcity has become a significant issue in the European Union (EU) during 21st Century, due to its relevance as an irreplaceable macronutrient for life, and because of the total dependency of EU regarding imports. This work aims to evaluate the phosphorus recovery by adsorption in batch and fixed-bed column, using a thermally modified eggshell as an adsorbent. The screening phase revealed that calcined eggshell at 700 °C (CES700) is the most suitable material compared with the other thermally modified eggshells tested. Thus, CES700 was characterized regarding the specific surface area, pore volume, zero-point charge pH, total dissolved solids and organic matter. The influence of pH and adsorbent dosage was investigated in batch conditions. Langmuir-Freundlich model described the equilibrium data and the maximum adsorption capacity was about 39 mg P-PO4/g. The kinetics follows a pseudo-first order model, with constants between 0.063 and 0.224 min−1. Fixed-bed studies indicated that increasing fluid superficial velocity and feed concentration led to an early saturation of the adsorbent. Yoon-Nelson, Thomas and Bohard-Adams empirical models properly adjusted the breakthrough curves with R2 ≥ 0.98. Germination tests using CES700 loaded with phosphate revealed a germination index of 120 and 124% to 48 and 72 h, respectively. CES700 is statically better than the other tested materials, which opens the possibility of its use as fertilizer. This study showed that the developed material, CES700, can be applied in batch or fixed-bed processes to recover phosphate ions from liquid effluents, and the loaded adsorbent has potential to be further used as fertilizer.

Biochemical methane potential (BMP) corresponds to the maximum methane production at anaerobic digestion infinite time and is a key parameter to evaluate the suitability of substrates to obtain biogas. The main objective of this work is to explore the data available in the literature for ten categories of substrates to compare and develop new methods and mathematical models able to predict BMP. Indeed, experimental procedure is time-consuming, laborious and costly, and the development of methods or models based on properties easily assessed may be very helpful at industrial scale. In this study, three substrates (banana waste, tomato waste and winery wastewater) were tested and compared with >150 results from the literature. The analysis involved four methods (Met_I to Met_IV) and five models developed by multivariate regression (Mod_I to Mod_V). Met_I is related to elemental analysis; Met_II with the organic fraction composition; Met_III is associated with chemical oxygen demand (COD); Met_IV is based on NIR spectra. Regression models are combinations by grouping single variables: C, H, O, N (Mod_I); hemicellulose, lignin (LG), acid detergent fibre (ADF) (Mod_II); volatile solids (VS), COD (Mod_III); proteins (PT), carbohydrates (CRB), lipids (LP) (Mod_IV); and CRB, LP, PT, LG, ADF (Mod_V). The results showed that no significant correlation can be found between BMP and single common properties (e.g. VS or C/N ratio). However, good results may be achieved with models developed by multivariate regression (R2 from 0.93 to 0.98, and R2adj from 0.91 to 0.96). The prediction of BMP based on Met_IV, which is based on NIR spectroscopy combined with a multivariate regression model, revealed to be a promising method for both data from literature as well as for substrates analyzed in the present work.

Environmental policies in the European Union focus on the prevention of hazardous waste and aim to mitigate its impact on human health and ecosystems. However, progress is promoting a shift in perspective from environmental impacts to resource recovery. Municipal solid waste incineration (MSWI) has been increasing in developed countries, thus the amount of air pollution control residues (APCr) and fly ashes (FA) have followed the same upward trend. APCr from MSWI is classified as hazardous waste in the List of Waste (LoW) and as an absolute entry (19 01 07*), but FA may be classified as a mirror entry (19 0 13*/19 01 14). These properties arise mainly from their content in soluble salts, potentially toxic metals, trace organic pollutants and high pH in contact with water. Since these residues have been mostly disposed of in underground and landfills, other possibilities must be investigated to recover secondary raw materials and products. According to the literature, four additional routes of recovery have been found: detoxification (e.g. washing), product manufacturing (e.g. ceramic products and cement), practical applications (e.g. CO2 sequestration) and recovery of materials (e.g. Zn and salts). This work aims to identify the best available technologies for material recovery in order to avoid landfill solutions. Within this scope, six case studies are presented and discussed: recycling in lightweight aggregates, glass-ceramics, cement, recovery of zinc, rare metals and salts. Finally, future perspectives are provided to advance understanding of this anthropogenic waste as a source of resources, yet tied to safeguards for the environment.

Free air space (FAS) is a physical parameter that can play an important role in composting processes to maintain favourable aerobic conditions. Aiming to predict the FAS of initial composting mixtures, specific materials proportions ranged from 0 to 1 were tested for a case study comprising industrial potato peel, which is characterized by low air void volume, thus requiring additional components for its composting. The characterization and prediction of FAS for initial mixtures involving potato peel, grass clippings and rice husks (set A) or sawdust (set B) was accomplished by means of an augmented simplex-centroid mixture design approach. The experimental data were fitted to second order Scheffe polynomials. Synergistic or antagonistic effects of mixture proportions in the FAS response were identified from the surface and response trace plots in the FAS response. Moreover, a good agreement was achieved between the model predictions and supplementary experimental data. Moreover, theoretical and empirical approaches for estimating FAS available in literature were compared with the predictions generated by the mixture design approach. This study demonstrated that the mixture design methodology can be a valuable tool to predict the initial FAS of composting mixtures, specifically in making adjustments to improve composting processes containing primarily potato peel.

This study aims to evaluate a new biosorbent derived from co-composting eggshell with other organic materials (potato peels, grass clipping, and rice husk) for uptaking Pb(II) from an aqueous medium. This biosorbent contains a high amount of eggshell (30 % w/w; CES) and its performance was compared to mature compost without eggshell (CWES) and natural eggshell (ES). Sorption kinetics and equilibrium data were fitted to pseudo-second-order and Langmuir models, respectively. From a kinetic point of view, lead sorption into CES was fast, attaining equilibrium within less than 180 min. Batch experiments indicated that maximum sorption capacity of Pb into CES is 23 mg g−1. The sorption capacity of CES was not significantly dependent on pH within the range of 2–5.5. In comparison to ES, organic matter of CES provided supplementary sites for lead sorption and an increase of 43 % in the sorption capacity was observed. Nevertheless, CWES was the biosorbent with higher sorption capacity. Still, this study points out the potential of new use of CES as an effective biosorbent to lead removal from aqueous matrices.

In this study two chelating resins containing iminodiacetic acid groups (Amberlite IRC 748 and Diaion CR 11) and a chelating resin based on sulfonic and diphosphonic acid groups (Diphonix) were investigated in order to separate Cr(III) from industrial effluents produced in hard and decorative electroplating. Samples of two industrial plants were characterized during a period of about one year and a half in terms of the metals content (Cr, Cu, Na, Ca, Fe and Ni), Total Suspended Solids (TSS), Total Dissolved Solids (TDS), Chemical Oxygen Demand (COD) and pH. Some of the physical properties of the resins, namely the moisture content, apparent density, intraparticle porosity and the particle size distribution were also evaluated. To quantify the sorption capacity of the resins, batch experiments were performed using synthetic solutions of Cr(III), as well as solutions of Fe in the case of Diphonix. The Langmuir and Langmuir-Freundlich isotherms enabled a good description of the ion-exchange equilibrium data, and the maximum sorption capacity determined for Amberlite and Diaion was 3.6 mequiv./g(dry resin). For Diphonix that parameter was 3.4 mequiv./g(dry resin). The Diphonix resin exhibits a high selectivity for transition metals (Fe, Ni) over the chromium trivalent. Therefore, it was screened as the most suitable for selectively removing those metal impurities from chromium electroplating effluents. For this resin, the sorption capacity is strongly dependent on the initial pH of the solution. Though, high regeneration efficiencies of Diphonix for stripping Cr(III) were found by using a mixture of NaOH/H(2)O(2). The mathematical model tested for describing the dynamics of the process allowed a good fitting to the experimental data and enabled the estimation of effective pore diffusivity of Cr(III). The saturations of Diphonix with industrial effluents demonstrated that the breakthrough capacity of the resin is affected by the presence of other species in solution, such as Fe and Ni. Nevertheless, these effluents may be treated with this resin, being possible to separate Cr(III) from other transition metallic ions in solution.

This study aims to investigate the co-composting of an inorganic industrial waste (eggshell - ES) in very high levels (up to 60% w/w). Since composting is a process in which solid, liquid and gaseous phases interact in a very complex way, there is a need to shed light on statistical tools that can unravel the main relationships structuring the variability associated to this process. In this study, PCA and data visualisation were used with that purpose. The co-composting tests were designed with increasing quantities of ES (0, 10, 20, 30 and 60%ES w/w) mixed with industrial potato peel and rice husks. Principal component analysis showed that physical properties like free air space, bulk density and moisture are the most relevant variables for explaining the variability due to ES content. On the other hand, variability in time dynamics is mostly driven by some chemical and phytoxicological parameters, such as organic matter decay and nitrate content. Higher ES incorporation (60% ES) enhanced the initial biological activity of the mixture, but the higher bulk density and lower water holding capacity had a negative effect on the aerobic biological activity as the process evolved. Nevertheless, pathogen-killing temperatures (>70°C for 11h) were attained. All the final products obtained after 90days were stable and non-phytotoxic. This work proved that valorisation of high amounts of eggshell by co-composting is feasible, but prone to be influenced by the physical properties of the mixtures.

This study aims to explore an innovative approach consisting of the Fenton’s process to stabilise organic wastes as an alternative to the traditional aerobic decomposition (composting). Digestate from the anaerobic digestion of the organic fraction of municipal solid wastes was taken from a mechanical–biological treatment plant and was thoroughly characterised regarding physical, chemical and biological properties. This sludge contained around 7.8 g Fe kg TS-1 , which can be beneficial to the chemical oxidation. However, the use of zero-valent iron nanoparticles or iron(II) salt revealed treatment can be improved by adding extra iron into the system. The response surface methodology determined that the best peroxidation conditions were 35.6 g H2O2 kg TS-1 and 33.1 g Fe2? kg TS-1 , while maintaining constant pH 3, L/S 5 and room temperature. The chemical treatment enhanced the stability, reducing the oxygen uptake rate from 4.63 to 2.57 g O2 kg VS-1 h-1 . Moreover, the germination index increased from 37 to 99.9 %, which means the treatment yielded a non-phytotoxic product. The outcomes of the present study are promising and open a new pathway for the Fenton peroxidation in semi-solid processes since this fast method can be very competitive when compared with the slow composting technology. info:eu-repo/semantics/publishedVersion

This study focuses on the stabilisation/solidification (S/S) treatment of air pollution control (APC) residues from municipal solid waste (MSW) incineration. Six formulations (T1–T6) were tested based on different cements as binders, for the immobilisation of pollutants and to prevent their entering into the environment at unacceptable rates. Soluble phosphates and silicates were considered in some cases to fix heavy metals. The performance of T1–T6 products was measured in terms of initial and final setting times, mechanical strength, total availability and leaching from S/S products. Two monolithic leaching tests were used to estimate emissions of pollutants over 48 h and 64 days. The results showed that the setting time was reduced when soluble phosphates were used. Moreover, although all the treatments have met the threshold of 1 MPa for unconfined compressive strength, this parameter was significantly reduced due to matrix dissolution during immersion. After three cycles of leaching, the limit of 10% for solubilisation was exceeded for all treatments with the exception of T5 (with phosphates). This study demonstrated that the S/S treatment used at the industrial level can be improved with respect to toxic heavy metals, by using soluble silicates or phosphates, but not regarding soluble salts.

Industrial eggshell waste (ES) is classified as an animal by-product not intended to human consumption. For reducing pathogen spreading risk due to soil incorporation of ES, sanitation by composting is a pre-treatment option. This work aims to evaluate eggshell waste recycling in self-heating composting reactors and investigate ES effect on process evolution and end product quality. Potato peel, grass clippings and rice husks were the starting organic materials considered. The incorporation of 30% (w/w) ES in a composting mixture did not affect mixture biodegradability, nor its capacity to reach sanitizing temperatures. After 25 days of composting, ES addition caused a nitrogen loss of about 10 g N kg−1 of initial volatile solids, thus reducing nitrogen nutritional potential of the finished compost. This study showed that a composting mixture with a significant proportion of ES (30% w/w) may be converted into calcium-rich marketable compost to neutralize soil acidity and/or calcium deficiencies.

The main objective of this study was to evaluate the feasibility of recycling large quantities of industrial eggshell waste through turned windrows composting in order to obtain a value-added soil improver. For that, four different formulations were tested to produce stable composts with adequate properties to be further used for agronomic applications such as amendment in soils with acid characteristics and/or with low calcium concentration. The eggshell waste is mainly an inorganic animal by-product, and thus its co-composting was conducted with farm wastes (horse and chicken manures) and grass clipping. The windrows were aerated periodically and monitored during 50 days regarding temperature, moisture, pH, conductivity, and carbon/nitrogen ratio (C/N). The thermophilic phase lasted for 10–20 days. At the end, moisture, pH, electrical conductivity, organic matter, C/N ratio, and toxic heavy metals (Cd, Cr, Pb, Cu, Ni, Zn) were determined. The microbiological assessment involved total mesophilic heterotrophic bacteria, total coliform bacteria, thermotolerant coliform bacteria, E.coli and spores of sulphite-reducing clostridia. The assessment of maturity based on germination index and stability by using Dewar self-heating test and respirometry showed that all the composts were mature and stable, with adequate properties for agronomic applications. This study evidenced that large quantities (up to 30 % in weight) of eggshell waste may be converted into calcium-rich marketable compost by thermophilic windrows composting.

This study aimed to assess the selective separation of Cr(III) from Fe(III) from liquid solutions by using a chelating ion exchange resin, Diaion CR 11, from Mitsubishi Chemical Corporation, in the H+ form. Equilibrium experiments with synthetic solutions of iron and chromium were carried out in batch mode. For both metals favorable adsorption isotherms were obtained, and the experimental data were well described by the Langmuir model. However, the resin exhibited higher affinity for iron than for chromium. The regeneration experiments revealed that, for both metals, HCl provided higher removal efficiencies than H2SO4 and HNO3. Moreover, precipitation with NaOH allows selectively separate chromium and iron to be stripped from the resin. Experiments in fixed bed operation were carried out to assess the dynamic behavior of the sorption of Cr(III) and Fe(III) into the tested resin by using synthetic and industrial solutions. The experiments with industrial effluent showed that the resin can remove low levels of contaminant transition metal ions, and thus the effluent can be purified for reuse of chromium during periods of 20–25 min. The resin regeneration was achieved with a sequential treatment with HCl and NaOH/H2O2. High efficiencies were observed for both monocomponent and multicomponent systems. A global strategy for separating and recovering Cr(III) from an effluent that also contains Fe(III) is presented, involving the integration of ion exchange (saturation and regeneration phases) and precipitation processes. In conclusion, our approach demonstrates that efficient separation of chromium and iron is possible if ion exchange operation in a fixed bed configuration is optimized and combined with conventional processes such as precipitation.

Composting is one of the technologies recommended for pre-treating industrial eggshells (ES) before its application in soils, for calcium recycling. However, due to the high inorganic content of ES, a mixture of biodegradable materials is required to assure a successful procedure. In this study, an adequate organic blend composition containing potato peel (PP), grass clippings (GC) and wheat straw (WS) was determined by applying the simplex-centroid mixture design method to achieve a desired moisture content, carbon: nitrogen ratio and free air space for effective composting of ES. A blend of 56% PP, 37% GC and 7% WS was selected and tested in a self heating reactor, where 10% (w/w) of ES was incorporated. After 29 days of reactor operation, a dry matter reduction of 46% was achieved and thermophilic temperatures were maintained during 15 days, indicating that the blend selected by statistical approach was adequate for composting of ES.

Taking into account current environmental concerns, the main objective of this work focused a national inventory aiming to estimate the amount of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) released in Portugal in 2006. The methodology used was based on the Standardized Toolkit for Identification and Quantification of Dioxins and Furan Releases, developed by UNEP Chemicals, in 2005. The method allows the assessment of the amount of PCDD/PCDF released into the environment along five vectors involving air, water, land, products and residues. Facing some difficulties mainly regarding to the availability of data for some activities known to produce PCDD/PCDF, three scenarios (Sc1 to Sc3) corresponding to lower, central and upper estimates were established. The Sc1 scenario (lower estimate) includes the situations where in case of doubt or scarce information, reduced or none emission values were assumed, Sc2 refers to a central estimate, which is believed to be the most realistic for the Portuguese situation, while Sc3 corresponds to the worst case (upper estimate). The results obtained pointed out that the total amount of PCDD/PCDF emitted in Portugal during the period under analysis was in the range of 51.2-217.9 g TEQ year(-1), with the most likely value of 95.2 g TEQ year(-1) achieved under the Sc2 scenario. This study also showed that the methodology developed by UNEP Chemicals is a very simple one, and the main difficulty is the availability of data. The main indicators calculated in this study were 8.98 μg TEQ/(year person) by taking into account the total amount of PCDD/PCDF released, and 3.63 μg TEQ/(year person) when only air emissions were considered.

In this study, percolation and batch leaching tests were considered in order to characterize the behaviour of air pollution control (APC) residues produced in a municipal solid waste incinerator (MSWI) as a function of the liquid to solid ratio (L/S). This waste is hazardous, and taking into account their physical and chemical properties, leaching of contaminants into the environment is the main concern. In our work the leaching behaviour of toxic heavy metals (Pb, Zn, Cr, Ni and Cu) and inorganics associated with soluble salts (Na, K, Ca and Cl) was addressed. Although pH of the leaching solution is the most important variable, L/S may also play an important role in leaching processes. In our work, results from column and batch tests were compared in terms of concentration (mg/L) and releasing (mg/kg). The APC residues revealed to be hazardous according to both tests, and both Pb and Cl(-) far exceeded the regulatory thresholds. The material exhibits high solubility, and when the liquid to solid ratio was high, more than 50% can be solubilised. The patterns of release may be in some cases availability or solubility controlled, and the former was easier to identify. When the results from column and batch experiments were compared by representing the cumulative released amounts (in mg/kg) as a function of L/S, both curves match for Zn, Ni, Cu, K, Na, Cl and Ca, but for Cr and Pb a significant difference was observed. In fact, the column experiments revealed that under percolation conditions it should be expected slow releasing of Pb along time. From this study, it can be concluded that the released amounts obtained in batch experiments for a certain L/S should be considered as the worst case for medium term. Some simple models proposed on the literature and based on local equilibrium assumption showed good fitting to experimental data for soluble species (non-reactive solutes).

Waste management and environmental protection are mandatory requirements of modern society. In our study, air pollution control (APC) residues from municipal solid waste incinerators (MSWI) were considered as a mixture of fly ash and fine particulate solids collected in scrubbers and fabric filters. These are hazardous wastes and require treatment before landfill. Although there are a number of treatment options, it is highly recommended to find practical applications rather than just dump them in landfill sites. In general, for using a construction material, beyond technical specifications also soil and surface water criteria may be used to ensure environmental protection. The Dutch Building Materials Decree (BMD) is a valuable tool in this respect and it was used to investigate which properties do not meet the threshold criteria so that APC residues can be further used as secondary building material. To this end, some scenarios were evaluated by considering release of inorganic species from unmoulded and moulded applications. The main conclusion is that the high amount of soluble salts makes the APC residues a building material prohibited in any of the conditions tested. In case of moulding materials, the limits of heavy metals are complied, and their use in Category 1 would be allowed. However, also in this case, the soluble salts lead to the classification of "building material not allowed". The treatments with phosphates or silicates are able to solve the problem of heavy metals, but difficulties with the soluble salts are still observed. This analysis suggests that for APC residues to comply with soil and surface water protection criteria to be further used as building material at least a pre-treating for removing soluble salts is absolutely required.

This study is mainly related with the physical and chemical characterization of a solid waste, produced in a municipal solid waste (MSW) incineration process, which is usually referred as air pollution control (APC) residue. The moisture content, loss on ignition (LOI), particle size distribution, density, porosity, specific surface area and morphology were the physical properties addressed here. At the chemical level, total elemental content (TC), total availability (TA) and the leaching behaviour with compliance tests were determined, as well as the acid neutralization capacity (ANC). The main mineralogical crystalline phases were identified, and the thermal behaviour of the APC residues is also shown. The experimental work involves several techniques such as laser diffraction spectrometry, mercury porosimetry, helium pycnometry, gas adsorption, flame atomic absorption spectrometry (FAAS), ion chromatography, scanning electron microscopy (SEM), X-ray fluorescence (XRF), X-ray diffraction (XRD) and simultaneous thermal analysis (STA). The results point out that the APC residues do not comply with regulations in force at the developed countries, and therefore the waste should be considered hazardous. Among the considered heavy metals, lead, zinc and chromium were identified as the most problematic ones, and their total elemental quantities are similar for several samples colleted in an industrial plant at different times. Moreover, the high amount of soluble salts (NaCl, KCl, calcium compounds) may constitute a major problem and should be taken into account for all management strategies. The solubility in water is very high (more than 24% for a solid/liquid ratio of 10) and thus the possible utilizations of this residue are very limited, creating difficulties also in the ordinary treatments, such as in solidification/stabilization with binders. http://www.sciencedirect.com/science/article/B6TGF-4P8B11J-2/1/9f18dd5ebf0d0c65eb7c1fee9684f7f5