Mini-review: Nanoparticles for enhanced biogas upgrading.

This mini-review is intended to explore the innovative applications of nanoparticles (NPs) in biogas upgrading, emphasizing their capacity to enhance biogas quality. Numerous studies underscore how NPs, when applied during anaerobic digestion, can boost not only the quantity but also the quality of the produced biogas, leading to reduce significantly the concentration of hydrogen sulphide or even to remove it completely. Moreover, NPs are proving to be excellent alternatives as adsorbent materials, achieving up to 400 mgH2S g-1 NPs. In addition, new studies are exploring the application of NPs to increase the efficiency of biological treatments thanks to their unique features. This review also emphasizes the potential benefits and addresses the challenges that need to be overcome for these technologies to reach their full potential, ultimately contributing to the development of a sustainable and environmentally friendly energy landscape.

Evaluation of thermal drying for the recycling of flexible plastics.

The drying of flexible plastic waste is a current industrial problem in the plastic recycling sector. The thermal drying of plastic flakes is considered the most expensive and the most energy-consuming step in the recycling chain, which represents an environmental issue. This process is already present on the industrial scale but not well described in the literature. A better understanding of this process for this material will lead to the design of environmentally efficient dryers with an improved performance. The objective of this research was to investigate the behavior of flexible plastic in a convective drying process at a laboratory scale. The focus was to study the factors affecting this process such as velocity, moisture, size and thickness of the plastic flakes in both fixed and fluidized bed systems and to develop a mathematical model for predicting the drying rate considering heat and mass transfer of convective drying. Three models were investigated: the first one was based on a kinetic correlation of the drying, and the second and third models were based on heat and mass transfer mechanisms, respectively. It was found that heat transfer was the predominant mechanism of this process, and the prediction of the drying was possible. The mass transfer model, on the other hand, did not give good results. Amongst five semi-empirical drying kinetic equations, three equations (Wang and Singh, logarithmic and 3rd-degree polynomial) provided the best prediction for both fixed and fluidized bed systems.

Heavy metals, PAHs and POPs in recycled polyethylene samples of agricultural, post-commercial, post-industrial and post-consumer origin.

In the present work, recycled polyethylene (LDPE) samples of agricultural, post-commercial, post-industrial and post-consumer origin were selected and analysed. The analysis comprised the determination of different contaminants such as metals, polycyclic aromatic hydrocarbons (PAHs), dioxin-like biphenyl polychlorides (PCBs), and polychlorinated-dibenzo-p-dioxins and furans (PCDD/Fs). A comparison with one sample of virgin plastic (unrecycled) was performed. The study aimed at stressing the importance of this type of analysis in recycled plastics. Indeed, such an examination will determine the material's final destination, and the possible origin of the pollutants analysed is investigated. Black post-industrial and post-consumer samples presented the highest concentration of PCBs and PCDD/Fs, attaining a maximum value of 2.40 pg WHO-TEQ/g, while the least toxic sample (post-commercial) presented a toxicity of 0.38 pg WHO-TEQ/g. PAHs content was also much higher in black samples, reaching 514.41 ng/g, while the lowest concentrations were obtained for the post-commercial plastic sample, which did not exceed 38.98 ng/g. The higher PAHs concentrations in the black samples were related to the carbon black content of the black samples, which was 2.00% for black post-industrial sample and 1.51% for post-consumer sample. The PCDD/Fs congener profile observed in almost all samples was very similar to the profile found in the literature on urban air samples, indicating that the plastic is mainly influenced by the environment. The presence of some metals (mainly copper) showed a slight correlation with PCDD/Fs content. The pollutants analysed were found to be significantly reduced during the cleaning processes that are generally carried out in recycling companies.

Presence of microplastics in commercial canned tuna.

The present study aims to determine the presence of synthetic polymeric microparticles (MPs) in samples of canned tuna. An analysis procedure of these microparticles was developed and tested. Four brands of tuna marketed in Ecuador canned both in water and oil were analysed. A significant presence of MPs was found: 692 ± 120 MPs/100 g of tuna in water and 442 ± 84 MPs/100 g of tuna in oil. Random samples of the liquid covering the tuna fish in the cans showed 6 MPs/mL in the case of water and 5 MPs/mL in the case of oil-containing samples. A total of 90% of the reported particles presented a size range of 1-50 µm. The number of MPs present in canned tuna suggests that the ingredients and inputs of the canning process greatly contribute to micro polymers. The identification of the microparticles using fluorescence and micro-FTIR spectrometry revealed that PET, polystyrene and nylon were the most frequent MPs present in the samples analysed.

Role of Gallic Acid in the Synthesis of Carbon-Encapsulated Iron Nanoparticles by Hydrothermal Carbonization: Selecting Iron Oxide Composition.

In this work, the role of phenolic compounds in the hydrothermal synthesis of carbon-encapsulated iron nanoparticles (CEINs) was studied. To model phenolic compounds, gallic acid (GA) was selected, with glucose as the carbon source. Iron was found as α-Fe2O3, γ-Fe2O3, Fe3O4, and zero-valent iron (ZVI) depending on the synthesis pH and GA/Fe molar ratio. For GA/Fe = 1, the CEINs' yield increased significantly. In the samples with phenolics, increasing the initial pH increased the amount of γ-Fe2O3 and Fe3O4 and enhanced the iron oxide encapsulation due to enhanced chelating ability. Reducing the GA/Fe ratio to 0.2 resulted in CEINs with stronger magnetization due to the presence of Fe3O4. Ash weight, HCl digestion, and Raman spectroscopy were used in conjunction to characterize the composition of the CEINs. The magnetization of the samples was compared using a simple magnetic weight setup. A scheme for the reactions occurring during the hydrothermal carbonization of GA-Fe complexes was proposed.

Heterogeneous Fenton Degradation of Patulin in Apple Juice Using Carbon-Encapsulated Nano Zero-Valent Iron (CE-nZVI).

Patulin (PAT), a mycotoxin found mainly in matured apples, is produced by different species of fungi, mainly Penicillium expansum, and is found in various fruits and vegetables used to produce juice. Little focus has been placed on nano-technological methods for the mitigation of this problem. In this work, carbon-encapsulated nano-zero valent iron (CE-nZVI) particles were synthesized and used as heterogeneous Fenton agents for the degradation of PAT in apple juice. The particles were found to have a spherical shape with a diameter of 130 ± 50 nm. In a heterogeneous Fenton degradation (involving CE-nZVI) process, a concentration of 0.05 g/L CE-nZVI with 0.5 mM H2O2 was used. Since the Fenton oxidation process is pH-dependent, placebo degradation was observed at varying pH conditions with an average percentage of PAT degradation of 27.8%, 87.0%, 98.0%, and 99.75% at pH 6, 5, 4.5, and 3.5 respectively, between 1 min to 4 h in a water matrix. In a juice matrix, at the regular pH of juice (3.6), percentage PAT degradation of 72% and 89% was obtained after a 2-h treatment using heterogeneous Fenton oxidation (CE-nZVI/H2O2) systems, using 0.5 mM H2O2 and 1 mM H2O2, respectively.

Odorant composition of post-consumer LDPE bags originating from different collection systems.

The establishment of recycling systems aiming at high-quality recyclates from post-consumer plastic waste are essential to avoid the waste of resources. One main impediment for introducing recyclates into the market is their unwanted odor. For this reason, this study aimed at determining if the collection strategy affects the odor profile of post-consumer LDPE bags. Furthermore, the effect of hot water washing, inspired by the conventional mechanical recycling procedure, on the odor of post-consumer LDPE bags was screened. More than 60 odorants were detected in LDPE bags collected in a separate plastic fraction as well as in LDPE bags from the non-separated collection by means of gas chromatography-olfactometry, and 37 of them were unequivocally identified using two-dimensional gas chromatography-mass spectrometry/olfactometry. The sensory results revealed that the type of collection affects the overall odor intensity, the hedonic tone of the odor and the odor profile. Namely, cheesy and fecal smelling odorants were predominant in the waste that had not been separated at source, whereas odorants with earthy and moldy smells showed mostly higher intensity ratings in the waste separated at source. Short chain carboxylic acids, likely originating from microbial spoilage of organic waste, were found with higher dilution factors in the mixed fraction, and could, accordingly, contribute to the observed differences. Additionally, we could show that the hot washing procedure, applied to the LDPE sample from the separate collection system, significantly reduced the overall odor intensity from 8 to 6.3 (0-10 scale). However, the washed waste still showed high smell intensity ratings.

Recyclability of four types of plastics exposed to UV irradiation in a marine environment.

Plastics are the most abundant products in the world and therefore also represent the largest volume of materials found in the sea. Their resistance to degradation makes them dangerous for the marine environment. In this study, the degradation of the four main plastics (Nylon, Polyethylene (PE), Polypropylene (PP), Polyethylene terephthalate (PET)) found in the sea was observed for 6.5 months as they were exposed to UV irradiation in a marine environment. Data on changes in the physical and chemical properties of each of them were collected in order to evaluate the possibilities of material (mechanical) recycling. A thermobalance was used to look for differences in the thermal decomposition of the plastics during this time. In addition, the mechanical properties of each plastic were studied. Results showed that both thermal and mechanical properties were affected, causing a weakening of the material which became less elastic and more rigid. Furthermore, SEM and AFM images were obtained: they showed cracks, flakes and granular oxidation as well as a loss of homogeneity on the surface of the samples. These changes make mechanical recycling unfeasible, since the quality of the recycled material is insufficient to ensure a high virgin material substitution rate.

Author Correction: Microplastics in Spanish Table Salt.

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Microplastics in Spanish Table Salt.

Marine debris is widely recognized as a global environmental problem. One of its main components, microplastics, has been found in several sea salt samples from different countries, indicating that sea products are irremediably contaminated by microplastics. Previous studies show very confusing results, reporting amounts of microparticles (MPs) in salt ranging from zero to 680 MPs/kg, with no mention of the possible causes of such differences. Several errors in the experimental procedures used were found and are reported in the present work. Likewise, 21 different samples of commercial table salt from Spain have been analyzed for MPs content and nature. The samples comprise sea salts and well salts, before and after packing. The microplastic content found was of 50-280 MPs/kg salt, being polyethylene-terephthalate (PET) the most frequently found polymer, followed by polypropylene (PP) and polyethylene (PE), with no significant differences among all the samples. The results indicate that even though the micro-particles might originate from multiple sources, there is a background presence of microplastics in the environment.

Study of the presence of PCDDs/PCDFs on zero-valent iron nanoparticles.

Studies show that nanoscale zero-valent iron (nZVI) particles enhance the formation of chlorinated compounds such as polychlorinated dioxins and furans (PCDD/Fs) during thermal processes. However, it is unclear whether nZVI acts as a catalyst for the formation of these compounds or contains impurities, such as PCDD/Fs, within its structure. We analyzed the presence of PCDD/Fs in nZVI particles synthesized through various production methods to elucidate this uncertainty. None of the 2,3,7,8-substituted congeners were found in the commercially-produced nZVI, but they were present in the laboratory-synthesized nZVI produced through the borohydride method, particularly in particles synthesized from iron (III) chloride rather than from iron sulfate. Total PCDD/F WHO-TEQ concentrations of up to 35 pg/g were observed in nZVI particles, with hepta- and octa-chlorinated congeners being the most abundant. The reagents used in the borohydride method were also analyzed, and our findings suggest that FeCl3 effectively contains PCDD/Fs at concentrations that could explain the concentrations observed in the nZVI product. Both FeCl3 and nZVI showed a similar PCDD/F patterns with slight differences. These results suggest that PCDD/Fs might transfer from FeCl3 to nZVI during the production method, and thus, care should be taken when employing certain nZVI for environmental remediation.

Predicting the drying properties of sludge based on hydrothermal treatment under subcritical conditions.

The effects of hydrothermal treatment on the drying properties of sludge were determined. Sludge was hydrothermally treated at 180-260 °C for 0.5-5 h using NaOH and HCl as additives to influence reaction conditions. Untreated sludge and attained hydrochar samples were then dried under identical conditions with a laboratory microdryer and an X-ray microtomograph was used to follow changes in sample dimensions. The effective moisture diffusivities of sludge and hydrochar samples were determined and the effect of process conditions on respective mean diffusivities evaluated using multiple linear regression. Based on the results the drying time of untreated sludge decreased from approximately 80 min to 37-59 min for sludge hydrochar. Drying of untreated sludge was governed by the falling rate period where drying flux decreased continuously as a function of sludge moisture content due to heat and mass transfer limitations and sample shrinkage. Hydrothermal treatment increased the drying flux of sludge hydrochar and decreased the effect of internal heat and mass transfer limitations and sample shrinkage especially at higher treatment temperatures. The determined effective moisture diffusivities of sludge and hydrochar increased as a function of decreasing moisture content and the mean diffusivity of untreated sludge (8.56·10(-9) m(2) s(-1)) and sludge hydrochar (12.7-27.5·10(-9) m(2) s(-1)) were found statistically different. The attained regression model indicated that treatment temperature governed the mean diffusivity of hydrochar, as the effects of NaOH and HCl were statistically insignificant. The attained results enabled prediction of sludge drying properties through mean moisture diffusivity based on hydrothermal treatment conditions.

Hydrothermal carbonization of industrial mixed sludge from a pulp and paper mill.

Mixed sludge from a pulp and paper mill was hydrothermally carbonized at 180-260°C for 0.5-5h with the use of HCl or NaOH for determining the effect of acid and base additions during sludge carbonization. Based on the results carbonization was mainly governed by dehydration, depolymerization and decarboxylation of sludge components. Additive type had a statistically significant effect on hydrochar carbon content and carbon and energy yield, of which especially energy yield increased through the use of HCl. The theoretical energy efficiencies of carbonization increased with decreasing reaction temperature, retention time and the use of HCl and suggested that the energy requirement could be covered by the energy content of attained hydrochar. The BOD5/COD-ratios of analyzed liquid samples indicated that the dissolved organic components could be treated by conventional biological methods.

Heavy metal release due to aging effect during zero valent iron nanoparticles remediation.

Zero valent iron nanoparticles (nZVI) represent a promising agent for environmental remediation. Nevertheless, their application presents some limitations regarding their rapid oxidation and aggregation in the media. The aim of this study was to determine the effect that nZVI aging has in heavy metal remediation in water. Contaminants studied were Zn, Cd, Ni, Cu and Cr, which are typical elements found in ground and wastewater. Results show a high contaminant removal capacity by the nZVI in the first 2 h of reaction. Nevertheless, for longer reaction times, some of the metal ions that had already been adsorbed in the nZVI were delivered to the water. Cd and Ni show the maximum delivery percentages (65 and 27% respectively after 21 days of contact time). The starting delivery time was shortened when applying lower nZVI amounts. No re-dissolution of Cr was observed in any circumstance because it was the only element incorporated into the nanoparticles core, as TEM images showed. Contaminant release from nZVI is probably due to nanoparticles oxidation caused by aging, which produced a pH decrease and nZVI surface crystallization.

Viability study of automobile shredder residue as fuel.

Car Fluff samples collected from a shredding plant in Italy were classified based on particle size, and three different size fractions were obtained in this way. A comparison between these size fractions and the original light fluff was made from two different points of view: (i) the properties of each size fraction as a fuel were evaluated and (ii) the pollutants evolved when each size fraction was subjected to combustion were studied. The aim was to establish which size fraction would be the most suitable for the purposes of energy recovery. The light fluff analyzed contained up to 50 wt.% fines (particle size<20 mm). However, its low calorific value and high emissions of polychlorinated dioxins and furans (PCDD/Fs), generated during combustion, make the fines fraction inappropriate for energy recovery, and therefore, landfilling would be the best option. The 50-100 mm fraction exhibited a high calorific value and low PCDD/F emissions were generated when the sample was combusted, making it the most suitable fraction for use as refuse-derived fuel (RDF). Results obtained suggest that removing fines from the original ASR sample would lead to a material product that is more suitable for use as RDF.

Low temperature thermal degradation of PCDD/Fs in soil using nanosized particles of zerovalent iron and CaO.

This study investigated the degradation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in contaminated soil using low temperature treatment (200-280°C) both alone and in combination with nanosized zerovalent iron (nZVI) particles or CaO. Control soil samples and soil fortified with nZVI particles or CaO were treated at 200 and 250°C in sealed glass ampoules. Treatment of the ampouled samples at 250°C was more effective than treatment at 200°C and the reduction in PCDD/F concentration was greatest when soil was treated at 250°C with nZVI addition (indeed, treatment at 200°C in the absence of nZVI resulted in increases in total PCDD and PCDD/F concentrations). In larger-scale experiments based on the obtained results, using a rotary furnace, the greatest reduction in total PCDD/F concentration was achieved by treating soil at 280°C, and adding nZVI to the soil resulted in almost no detectable PCDD/F in the gas phase.

Formation of polychlorinated compounds in the combustion of PVC with iron nanoparticles.

The influence of iron nanoparticles in the fuel-rich combustion of PVC has been studied in this work. Dynamic runs for PVC and the mixture PVC and iron nanoparticles were firstly carried out by TGA-MS in order to study the influence of iron on the compounds evolved in the thermal degradation of PVC. To complete the study both PVC and a mixture of PVC and iron nanoparticles were burnt in a laboratory reactor under two different operating conditions: at 850 degrees C and in two stages, the first one at 375 degrees C and the resulting char cooled and subsequently burnt at 850 degrees C. Carbon oxides, light hydrocarbons, PAHs, chlorophenols, chlorobenzenes and PCDD/Fs were analyzed. It was observed that the mixture of PVC with iron nanoparticles at 375 degrees C greatly enhances the formation of light hydrocarbons and polychlorinated compounds, probably indicating that the presence of iron during the thermal decomposition of PVC causes the formation of iron chloride which may have a high catalytic effect.

Decomposition of paper wastes in presence of ceramics and cement raw material.

Paper recycling is an environmental important activity that is carried out in all the countries, but during the recycling process a paper waste is produced. Generally these wastes are placed in landfill sites but it is possible to profit it as secondary fuel and raw material in manufacture furnaces. In this work the combustion of the waste papers with cement and ceramic raw material has been studied with the objective to analyse the interaction of these substances with the emitted pollutants like PAHs and PCDD/Fs. The results of the study show that the presence of inorganic material produces an increment in the lighter PAH emission but chlorinated compounds are not affected. The PCDD/F emission level found in the combustion of this waste is quite low compared with other wastes subjected to similar conditions.

Remediation of PCB contaminated soils using iron nano-particles.

In this study, iron nano-particles were used to remediate PCB contaminated soil and an attempt was made to maximize PCB destruction in each treatment step. The results show that nano-particles do aid in the dechlorination process and high PCB destruction efficiencies can be achieved. The destruction efficiency during the preliminary treatment (mixing of soil and iron nano-particles in water) can be increased by increasing the water temperature. The maximum thermal destruction (pyrolysis/combustion of soil after preliminary treatment) of soil-bound PCBs occurs at 300 degrees C in air. A minimum total PCB destruction efficiency of 95% can be achieved by this process. The effect of changing treatment parameters such as type of mixing, time of mixing and mixing conditions and application of other catalysts like iron oxide and V(2)O(5)/TiO(2) was also investigated. It was found that at 300 degrees C in air, iron oxide and V(2)O(5)/TiO(2) are also good catalysts for remediating PCB contaminated soils.