COVID-19 personal protective equipment (PPE) contamination in coastal areas of Granada, Spain.

The use of disposable personal protective equipment (PPE) as a control measure to avoid transmission against COVID-19 has generated a challenge to the waste management and enhances plastic pollution in the environment. The research aims to monitor the presence of PPE waste and other plastic debris, in a time interval where the use of face mask at specific places was still mandatory, on the coastal areas of Granada (Spain) which belongs to the Mediterranean Sea. Four beaches called La Rijana, La Charca, La Rábita and Calahonda were examined during different periods. The total amount of sampled waste was 17,558 plastic units. The abundance, characteristics and distribution of PPE and other plastic debris were determined. Results showed that the observed amount of total plastic debris were between 2.531·10-2 and 24.487·10-2 units per square meter, and up to 0.136·10-2 for PPE debris, where face masks represented the 92.22 % of the total PPE debris, being these results comparable to previous studies in other coastal areas in the world. On the other hand, total plastic debris densities were in the range from 2.457·10-2 to 92.219·10-2 g/m2 and densities were up to 0.732·10-2 for PPE debris. PPE debris supposed 0.79 % of the weight of total waste and the 0.51 % of total items. Concerning non-PPE plastic waste: cigarettes filters, food containers and styrofoam were the most abundant items (42.95, 10.19 and 16.37 % of total items, respectively). During vacation periods, total plastic debris amount increased 92.19 % compared to non-vacation periods. Regarding type of beaches, the presence of plastic debris was significantly higher on touristic/recreational than in fishing beaches. Data showed no significant differences between accessible and no-accessible beaches, but between periods with restrictive policy about mask face use and periods with non-restrictive policy data suggest significant differences between densities (g/m2) for PPE litter. The amount of PPEs debris is also correlated with the number of cigarettes filters (Person's r = 0.650), food containers (r = 0.782) and other debris (r = 0.63). Finally, although interesting results were provided in this study, further research is required to better understand the consequences of this type of pollution and to provide viable solutions to this problem.

On the use of plastic precursors for preparation of activated carbons and their evaluation in CO2 capture for biogas upgrading: a review.

In circular economy, useful plastic materials are kept in circulation as opposed to being landfilled, incinerated, or leaked into the natural environment. Pyrolysis is a chemical recycling technique useful for unrecyclable plastic wastes that produce gas, liquid (oil), and solid (char) products. Although the pyrolysis technique has been extensively studied and there are several installations applying it on the industrial scale, no commercial applications for the solid product have been found yet. In this scenario, the use of plastic-based char for the biogas upgrading may be a sustainable way to transform the solid product of pyrolysis into a particularly beneficial material. This paper reviews the preparation and main parameters of the processes affecting the final textural properties of the plastic-based activated carbons. Moreover, the application of those materials for the CO2 capture in the processes of biogas upgrading is largely discussed.

Recovery, separation and production of fuel, plastic and aluminum from the Tetra PAK waste to hydrothermal and pyrolysis processes.

The establishment of a method of separation of materials from Tetra Pak waste to obtain products for use as raw material, fuel or other purposes was investigated in this study. First, the feasibility of hydrothermal treatment for the production of a solid fuel (hydrochar) and solid fraction formed by polyethylene and aluminum, called composite was analyzed. The results indicated that hydrothermal treatment performed at 240 °C yield the formation of hydrochar with good properties for its use as fuel and a composite of polyethylene and aluminum. The best conversion and separation of the cardboard and polyethylene/aluminum were obtained using 120 min as operating time. Then, the recovery of the aluminum fraction from the composite by using spent olive oil waste was studied. A partial separation of the composite layers (polyethylene and aluminum) was accomplished with improved aluminum purity for higher operating temperatures. Finally, the operating conditions of the pyrolysis process for the production of a solid (char) and high purity composite (aluminum) were optimized. The characterization results indicated that both char and aluminum resulting from the pyrolysis of the Tetra Pak at 400 °C still have a significant amount of polyethylene while higher purity levels of aluminum can be obtained at temperatures equal of higher than 500 °C.

Environmental status of marine plastic pollution in Spain.

The excessive use of plastic in our society is causing a massive accumulation, since it is a non-biodegradable product and with still poor recycling rates. This effect can be observed in the seas, which more and more plastic waste are accumulating. The present work is a critical review, based on all currently available literature, that reports environmental status of marine plastic pollution, especially microplastic pollution, in Spain. The three Spanish water areas with the highest presence of plastics are the Alboran Sea, the Gulf of Alicante and the vicinity of Barcelona probably related to fishing and industrial activities and high population densities. With regard to microplastic contamination on beaches in Spain, annual monitoring by the Spanish government shows contamination along the entire coast of the country, with particularly high concentrations in the Canary Islands (between 800 and 8800 particles/m2 in spring). Between 40 and 50% of the particles analyzed were pellets and the main factors postulated for the distribution of these particles are marine currents and the geomorphological characteristics. With regards to biota, ingestion of microplastics by fish has been intensely confirmed and, important differences were observed between the locations of the sampling, being bogues (Boops boops) one of the fish species more studied in Spain. Finally, the work includes a revision of European and Spanish legislation about plastics and marine pollution and some strategies to reduce this kind of contamination in Spain.

Microplastics and fibers from three areas under different anthropogenic pressures in Douro river.

Sources contributing to specific concentration of microplastics and fibers are still not completely understood. This study aimed at assessing the concentrations of microplastics (2-5000 µm) and fibers (18-5667 µm) in three areas of distinct influences in the Douro river, Porto, Portugal: (i) a countryside area; (ii) a wastewater treatment effluent release zone; and (iii) an area in proximity to a boat dock and maintenance station. Nile Red staining coupled with microscopy allowed the identification of small microplastics (≥2 µm) with a median concentration of the three areas of 231 MP L-1. Most were fragments (69%). Sizes <40 µm were the most abundant (84%). Highest concentrations of microplastics were found near the boat dock/maintenance and lowest in the countryside area. Fibers were mostly natural (non-synthetic, 63%). Highest concentrations of fibers were found in the area influenced by the wastewater effluent, especially of synthetic fibers, and lowest in the countryside area. Concentration of all fibers and synthetic fibers was 46 F L-1 and 6 F L-1, respectively. High concentrations of microplastics and fiber contamination suggest that the wastewater treatment plant effluent and boat dock/maintenance are the likely sources originating hotspot areas.

Liquid Hot Water Pretreatment and Enzymatic Hydrolysis as a Valorization Route of Italian Green Pepper Waste to Delivery Free Sugars.

In this work, liquid hot water pretreatment (autohydrolysis) was used to improve enzymatic hydrolysis of a commonly consumed vegetable waste in Spain, Italian green pepper, to finally produce fermentable sugars. Firstly, the effect of temperature and contact time on sugar recovery during pretreatment (in insoluble solid and liquid fraction) was studied in detail. Then, enzymatic hydrolysis using commercial cellulase was performed with the insoluble solid resulting from pretreatment. The objective was to compare results with and without pretreatment. The results showed that the pretreatment step was effective to facilitate the sugars release in enzymatic hydrolysis, increasing the global sugar yield. This was especially notable when pretreatment was carried out at 180 °C for 40 min for glucose yields. In these conditions a global glucose yield of 61.02% was obtained. In addition, very low concentrations of phenolic compounds (ranging from 69.12 to 82.24 mg/L) were found in the liquid fraction from enzymatic hydrolysis, decreasing the possibility of fermentation inhibition produced by these components. Results showed that Italian green pepper is an interesting feedstock to obtain free sugars and prevent the enormous quantity of this food waste discarded annually.

The potential of microplastics as carriers of metals.

Microplastics can adsorb chemical pollutants such as metals or pharmaceuticals, and transferred them along the food chain. In this work, an investigation of the adsorption of Cd, Co, Cr, Cu, Ni, Pb and Zn by five different types of microplastics was performed in Milli-Q water and natural waters (seawater, urban wastewater and irrigation water) via a series of batch adsorption experiments. The effects of concentration of metals and physicochemical characteristics of polymers were particularly studied. Results revealed a significant adsorption of lead, chromium and zinc on microplastics, especially on polyethylene and polyvinyl chloride. In the case of polyethylene terephthalate, it showed little adsorption capacity. Specific surface, porosity and morphology are characteristics that affect the molecular interactions. The adsorption isotherms were better described by Langmuir model, which indicates that the main adsorption mechanism might be chemical adsorption. Finally, results obtained in natural waters indicated that dissolved organic matter may play a major role on metal adsorption on microplastics. Results showed an enhancement of metal adsorption in waters with high chemical and biological oxygen demands as urban wastewater and irrigation water.

Physical-chemical characterization of microplastics present in some exfoliating products from Spain.

Plastic pollution in oceans is a global problem, with growing research efforts focusing on the threat of microplastics (<5 mm fractions). A source of microplastics pollution is derived from personal care products that contain polyethylene micro-spheres which are not captured by wastewater plants. In this work, ten personal care products (mainly scrubs) containing microplastics and marketed in Spain, were physico-chemically characterized. The obtained results proved that those microplastics had different particle size and are presented in high percentages in some cases, between 6 and 7% of the total product. Products with smaller particles usually showed higher concentrations than products with larger particles. Although all the microplastics were shown to be polyethylene, some impurities were observed that demonstrated the presence of silicates and oxides in the microplastics. Regards to morphology, the shape of the particles was irregular in general, although some completely spherical particles can be observed.

Removal of heavy metals from acid mining effluents by hydrolyzed olive cake.

The present study aims to solve two major challenges of the current society. On the one hand, it investigated the heavy metal removal from mining wastewater. On the other hand, it proposed an alternative use for olive cake. Firstly, a physic-chemical characterization of real wastewater and hydrolyzed olive cake was carried out. Secondly, a study of the affinity of the material for the different metals (chromium, manganese, copper, zinc, nickel and lead) was performed. The hydrolyzed olive cake showed a low content in ash (3.08%) and in water-soluble compounds (2.80%). The material presented the highest retention capacity for the lead (41.54 mg/g) and the lowest for the manganese (3.57 mg/g). After that, biosorption experiments in fixed-bed column were carried out using mining real water. In order to improve the biosorption capacity, the water pH was raised up to 6. The results were quite satisfactory with respect to others similar studies.

Kinetic study of thermal degradation of olive cake based on a scheme of fractionation and its behavior impregnated of metals.

This research aims to provide a better knowledge of the thermal decomposition of the olive cake as well as this lignocellulosic material loaded, in a previous stage of biosorption, with heavy metals for its use in processes of energy recovery. Firstly, isolation of constituents of the olive cake was carried out. Then, experiments were performed by thermogravimetric analysis (TGA) and differential thermogravimetry (DTG) under inert and oxidative atmosphere at a heating rate of 15 K/min for each isolated fraction. Next, adequate reactions schemes were proposed to find kinetic parameters. Validation of these schemes were verified by the goodness of fitting between experimental and simulated data. Also, some important combustion characteristics such as ignition and burnout temperatures were determined. With regard to the effect of metals, cadmium, copper, chromium, nickel and lead present in metal-loaded olive cake did not modify values of kinetic parameters which described the thermal decomposition processes.

Scale-up of a packed bed column for wastewater treatment.

After checking the success of the biosorption process to remove heavy metals from wastewater using olive tree pruning as a cheap biosorbent in the laboratory scale, the scale-up is necessary to progress towards industrial applications chance. The aim of this work was the study of the effect of scale-up in the process of biosorption of Pb(II) with olive tree pruning in a packed bed column. Experiments were performed using two different scale-up criteria and results obtained in both scales were compared. Similar parameters were obtained for each pair of equivalent tests, with a slightly advanced of the obtained breakthrough curves in the pilot plant. The experimental results were fitted by the Thomas model and the obtained mean values were KTh = 0.187 mL/min·mg and q0 = 20.59 mg/g for criterion 1 and KTh = 0.217 mL/min·mg and q0 = 20.27 mg/g for criterion 2. Finally, the mathematical model was applied to simulate industrial applications and it was obtained that under optimal operative conditions, a column according to the criterion 1 was able to operate 2.3 h, and a column according to the criterion 2 was able to operate for 3.6 h.

Neural fuzzy modelization of copper removal from water by biosorption in fixed-bed columns using olive stone and pinion shell.

Continuous copper biosorption in fixed-bed column by olive stone and pinion shell was studied. The effect of three operational parameters was analyzed: feed flow rate (2-6 ml/min), inlet copper concentration (40-100 mg/L) and bed-height (4.4-13.4 cm). Artificial Neural-Fuzzy Inference System (ANFIS) was used in order to optimize the percentage of copper removal and the retention capacity in the column. The highest percentage of copper retained was achieved at 2 ml/min, 40 mg/L and 4.4 cm. However, the optimum biosorption capacity was obtained at 6 ml/min, 100 mg/L and 13.4 cm. Finally, breakthrough curves were simulated with mathematical traditional models and ANFIS model. The calculated results obtained with each model were compared with experimental data. The best results were given by ANFIS modelling that predicted copper biosorption with high accuracy. Breakthrough curves surfaces, which enable the visualization of the behavior of the system in different process conditions, were represented.

Kinetic analysis of pyrolysis and combustion of the olive tree pruning by chemical fractionation.

This paper presents a kinetic analysis of thermal decomposition of olive tree pruning from its basic compounds in pyrolysis and combustion reactions. Experiments were performed by TGA under inert and oxidant conditions and results indicated that the decomposition of the olive tree pruning was related to the material composition. Pseudo-mechanistic models were proposed estimating the yield of pyrolysis on its basic compounds (hemicelluloses, cellulose and lignin). Validity and reliability of the proposed kinetic models were verified by the good fitting between the simulated and experimental curves (with values of R2 higher than 0.99 in most cases). Moreover, during the fractionation process, an acid fraction was obtained with great fuel properties, a high calorific value and a low residue after its combustion.

Volatile and semivolatile emissions from the pyrolysis of almond shell loaded with heavy metals.

Heavy metal-loaded almond shell was subjected to pyrolysis to understand the effect of the presence of different heavy metals on its thermal degradation. Pyrolysis behavior of native and metal-loaded samples was studied by thermogravimetric analysis. Similar shapes of thermogravimetric curves indicate that the presence of cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni) and lead (Pb) did not change the main degradation pathways of almond shell. However, the temperature at which the decomposition in each stage takes place at a higher rate and char yield was considerably modified by the presence of Cr and Ni. Then, pyrolysis tests of the almond shell samples were performed in a moving tubular reactor at 700°C. Gases and volatile organic compounds were collected using Tedlar bags and semivolatile organic compounds were collected using a resin as adsorbent. Significant changes were obtained in the composition of the gaseous fraction as a result of the metal impregnation. The main changes in the composition of the gas were observed for Ni-loaded sample, which presented the highest H2 and CO yields. Also, the yields of most of the light hydrocarbons decrease in the presence of metal, while the rest remain quite similar. The total PAH yields reached 103µg/g for nickel-loaded sample (NiAS), 164µg/g for copper-loaded sample (CuAS), 172µg/g for lead-loaded sample (PbAS), 245µg/g for native sample (AS), 248µg/g for cadmium-loaded sample (CdAS) and 283µg/g for chromium-loaded sample (CrAS). Nickel is the most effective in the higher aromatic tar reduction, followed by Cu and Pb, whereas the presence of Cd does not affect the total emissions of PAHs. Finally, the carcinogenic potency of the samples was calculated. Native sample and the sample loaded with Cr presented slightly higher values associated to the presence of small amounts of benzo(a)pyrene.

Combustion of a Pb(II)-loaded olive tree pruning used as biosorbent.

The olive tree pruning is a specific agroindustrial waste that can be successfully used as adsorbent, to remove Pb(II) from contaminated wastewater. Its final incineration has been studied in a thermobalance and in a laboratory flow reactor. The study aims at evaluating the fate of Pb during combustion, at two different scales of investigation. The flow reactor can treat samples approximately 10(2) larger than the conventional TGA. A detailed characterization of the raw and Pb(II)-loaded waste, before and after combustion is presented, including analysis of gas and solids products. The Pb(II)-loaded olive tree pruning has been prepared by a previous biosorption step in a lead solution, reaching a concentration of lead of 2.3 wt%. Several characterizations of the ashes and the mass balances proved that after the combustion, all the lead presents in the waste remained in ashes. Combustion in a flow reactor produced results consistent with those obtained in the thermobalance. It is thus confirmed that the combustion of Pb(II)-loaded olive tree pruning is a viable option to use it after the biosorption process. The Pb contained in the solid remained in the ashes, preventing possible environmental hazards.

Physico-chemical characterization of pine cone shell and its use as biosorbent and fuel.

Physico-chemical properties of pine cone shell have been determined. Results of characterization study showed that pine cone shell could be used as biosorbent of nickel from aqueous solutions in a fixed-bed column and later as input material in thermochemical processes. To study the behavior of Ni-loaded pine cone shell as fuel, non-isothermal thermogravimetric tests were performed. These tests showed that, in nitrogen atmosphere, the main decomposition occurs from 200°C to 500°C and, in oxidant atmosphere, the behavior is of type "combustion+pyrolysis" (at higher temperatures there is a clear decomposition of residue formed during the initial steps). Finally, the effect of the presence of Ni was analyzed. Thermogravimetric curves did not change their profile and the total amount of nickel was detected in char-ash fraction and not in flue gases. These results suggest that nickel does not form volatile compounds at considered operational conditions.

Comparative study of isotherm parameters of lead biosorption by two wastes of olive-oil production.

Batch isotherm studies were carried out on a laboratory scale: (i) to investigate the effectiveness to remove lead of two wastes (olive stone (OS) and olive tree pruning (OTP)), untreated and chemically treated; and (ii) to examine the applicability of various adsorption isotherms to fit the experimental data. Results from tests were analyzed using seven equilibrium isotherm correlations (Langmuir, Freundlich, Dubinin-Radushkevich, Temkin, Redlich-Peterson, Sips, and Toth equations). The sum of the squares of the errors was determined for each isotherm and the Langmuir equation provided the best fit. Chemical treatments increased the biosorption properties of these materials. The maximum biosorption capacities were: 6.33, 49.13, 14.83, and 38.93 mg g(-1) for untreated OS, HNO3-OS, H2SO4-OS, and NaOH-OS, respectively, and 26.72, 86.40, 72.78, and 123.80 mg g(-1) for untreated OTP, HNO3-OTP, H2SO4-OTP, and NaOH-OTP, respectively. Finally, the loss of mass for each waste (13.9, 14.3, and 36.8% for HNO3-OS, H2SO4-OS, and NaOH-OS and 35.1, 27.5, and 46.7% for HNO3-OTP, H2SO4-OTP, and NaOH-OTP, respectively) was taken into account and an effectiveness coefficient was determined for each adsorbent material.

Study of Cr (III) biosorption in a fixed-bed column.

This research analyzes the potential use of the olive stone as a low-cost biosorbent for Cr (III) from aqueous solutions in a continuous system. First, experiments were carried out in fixed-bed column to test the influence of various parameters on breakthrough and saturation time. The breakthrough and saturation time increase with the decrease of the flow rate. The same effect is shown when the bed depth is increased. The olive stone sorption capacity, q(e), increases as the inlet Cr (III) concentration increases until a value close to 0.800 mg/g is reached, then q(e) remains constant. Column data obtained at different conditions were described using the Adams-Bohart, Thomas, Yoon and Nelson, and Dose-Response models. The breakthrough curve prediction by the Adams-Bohart and Dose-Response models were found to be very satisfactory. In particular, the Adams-Bohart model can be used to represent the initial region of breakthrough curve, whereas the Dose-Response model is the one which best reproduces the whole curve for all the inlet Cr (III) concentrations used. Finally, a study of pH evolution was carried out. The pH increases at the beginning, subsequently decreasing as time passes until practically reaching the initial value.

Chemical treatment of olive pomace: effect on acid-basic properties and metal biosorption capacity.

In this study, olive pomace, an agricultural waste that is very abundant in Mediterranean area, was modified by two chemical treatments in order to improve its biosorption capacity. Potentiometric titrations and IR analyses were used to characterise untreated olive pomace (OP), olive pomace treated by phosphoric acid (PAOP) and treated by hydrogen peroxide (HPOP). Acid-base properties of all investigated biosorbents were characterised by two main kinds of active sites, whose nature and concentration were determined by a mechanistic model assuming continuous distribution for the proton affinity constants. Titration modelling denoted that all investigated biosorbents (OP, PAOP and HPOP) were characterised by the same kinds of active sites (carboxylic and phenolic), but with different total concentrations with PAOP richer than OP and HPOP. Single metal equilibrium studies in batch reactors were carried out to determine the capacity of these sorbents for copper and cadmium ions at constant pH. Experimental data were analysed and compared using the Langmuir isotherm. The order of maximum uptake capacity of copper and cadmium ions on different biosorbents was PAOP>HPOP>OP. The maximum adsorption capacity of copper and cadmium, was obtained as 0.48 and 0.10 mmol/g, respectively, for PAOP. Metal biosorption tests in presence of Na(+) in solution were also carried out in order to evaluate the effect of chemical treatment on biomass selectivity. These data showed that PAOP is more selective for cadmium than the other sorbents, while similar selectivity was observed for copper.