Experimental study, simulation and technical-economic feasibility of an interesterification plant for hydrocarbons synthesis by using plastics and frying oil waste.

This work presents the experimental assessment of a 20 mL batch reactor's efficacy in converting plastic and oil residues into biofuels. The reactor, designed for ease of use, is heated using a metallic system. The experiments explore plastic solubilization at various temperatures and residence times, employing a mixture of distilled water and ethylene glycol as the solvent. Initial findings reveal that plastic solubilization requires a temperature of 350 °C with an ethylene glycol mole fraction of 0.35, whereas 250 °C suffices with a mole fraction of 0.58. Additionally, the study includes a process simulation of a plant utilizing a double fluidized bed gasifier and an economic evaluation of the interesterification/pyrolysis plant. Simulation results support project feasibility, estimating a total investment cost of approximately $12.99 million and annual operating expenses of around $17.98 million, with a projected payback period of about 5 years.

The occurrence of pristine and functionalized fullerenes as constituents of airborne aerosols.

We investigated if pristine and functionalized fullerenes could be actual constituents of fine atmospheric aerosols. Comprehensive profiles of fullerenes from 1 µL extracts were made through matrix laser desorption ionization Time-of-Flight Mass Spectrometry (MALDI-MS) within a few minutes. The ion with m/z 720, corresponding to [C60]-•, was identified as fullerene after 1 µL of α-cyano-4-hydroxycinnamic acid matrix solution was spotted over the dried extracts. The ions with the m/z corresponding to C70, C76, C84, C100, C118, C128, and C130 were also attributed to other fullerene species detected within the samples. The ion m/z 878 was found to be the fullerene derivative diethyl methano[60]fullerene dicarboxylate. Since ions of fragmented fullerene molecules were not detected even at high laser energies, we considered the fullerenes' occurring as original constituents of real atmospheric particle matrices instead of being formed as artifacts of the laser action on samples. Therefore, this protocol would be helpful in the understanding of the distribution of either pristine or functionalized fullerenes in the environment and their participation in atmospheric chemistry under typical conditions, as well as its application in vitro and in vivo (eco)toxicity studies.

Green photocatalytic remediation of Fenthion using composites with natural red clay and non-toxic metal oxides with visible light irradiation.

In the present work, composites with non-toxic metal oxides, such as TiO2 and ZnO, and a natural red clay (taua) reach in hematite were used in the photocatalytic degradation of Fenthion. The composite TiO2/Taua (0.5:1 wt. ratio) and pure TiO2 were prepared by sol-gel method while ZnO/Taua (0.5:1 wt. ratio) and pure ZnO were prepared by Pechini method. The materials were characterized by XRD, SEM, EDX, and DRS. The anatase phase was formed in both pure TiO2 and TiO2/Taua, while the hexagonal phase was formed in pure ZnO and ZnO/Taua. The bandgap energies for the two composites were narrowed compared to the respective pure oxides as consequence of the hematite (α-Fe2O3, Eg = 2.1 eV) in the red clay, reaching 2.1 eV for TiO2/Taua and 2.0 eV for ZnO/Taua, while the bandgap energies for pure TiO2 and ZnO were 3.2 and 3.0 eV, respectively. Fenthion was not degraded in the dark, but the concentration droped 20% after 180 min under visible light irradiation without photocatalyst and 60% after 210 min in the presence of the pure red clay. Both TiO2/Taua and ZnO/Taua composites were also photocatalytic active to degrade Fenthion (λ > 420 nm), with degradation of 78% (in 180 min) and 85% (in 210 min) respectively. In the optimized conditions (pH 2, 100 mg L-1 of H2O2 and 30 mg L-1 of Fenthion), the ZnO/Taua composite was the most efficient, reaching 89% degradation in up to 30 min, with Fenthion sulfoxide as the degradation product.

Occurrence of mercury in polychaete species (Annelida) and their associated sediments from an important Southern Atlantic Ocean Bay.

In the present study, the Hg levels in freshly collected polychaete species and their associated sediments were evaluated from Todos os Santos Bay, Northeastern Brazil. Additionally, it was also measured the Hg distribution along the annelids' body parts (anterior region, abdomen, and posterior region). Total Hg concentration was as follows: 13.6-144 µg kg-1 (Scolelepis chilensis, deposit feeder), 8.2-122 µg kg-1 (Laeonereis acuta, deposit feeder), 95-612 µg kg-1 (Armandia agilis, deposit feeder); 96.6-206 µg kg-1 (Lumbrineris sp., carnivorous), 75.3-112 µg kg-1 (Goniada echinulate, carnivorous), and 115-198 µg kg-1 (Branchiomma sp., suspension feeder). In turn, Hg levels in sediments ranged from 2.77 ± 0.24 to 6.38 ± 0.15 µg kg-1. Hg concentrations found in polychaete soft tissues were higher than those found in the sediments. Specific habits, feeding behavior, trophic level, and stressful environmental conditions are the main factors affecting the Hg levels in the species studied. The bioaccumulation factor (BAF), contamination factor (CF), and ecological risk assessment (Er) were calculated. The BAF values were higher than 1 for all studied species, indicating Hg bioaccumulation in the annelids, but the low levels of CF e Er showed those Hg levels present low to no significant ecological risk for the biota and benthonic organisms living in the sediments. Finally, no statistically significant difference was observed for Hg concentration levels along the polychaete body parts.

Occurrence, sources, and risk assessment of unconventional polycyclic aromatic compounds in marine sediments from sandy beach intertidal zones.

This study investigated the concentrations of polycyclic aromatic compounds (PACs), including parent polyaromatic hydrocarbons (PAHs) and their nitrated and oxygenated derivatives, in 48 sediment samples from the intertidal region of sandy beaches in Baía de Todos os Santos (BTS), Salvador, State of Bahia, Brazil. The total PAH (∑PAH) concentration, total nitro-PAH (∑nitro-PAH) concentration, and total oxy-PAH (∑oxy-PAH) concentration ranged from 2.11 µg g-1 dry weight (dw) to 28.0 µg g-1 dw, 2.58 µg g-1 dw to 30.2 µg g-1 dw, and 0.34 µg g-1 dw to 3.65 µg g-1 dw, respectively. Elevated concentrations of parent PAHs and nitro-PAHs were found in samples from two sites in BTS, which were also characterized by high percentages of fine-medium sand and low organic matter contents. Potent mutagenic 3-nitrobenzanthrone (3-NBA) was found in 86% of the samples at concentrations ranging from 0.200 µg g-1 dw to 0.690 µg g-1 dw. Furthermore, calculations of the benzo[a]pyrene toxicity equivalency (BaPTEQ) indicated that three carcinogenic high-molecular-weight PAHs accounted for 98.7% of the total maximum PAH concentration. Finally, we assessed the possible environmental risks posed to benthic species living in the sediments of BTS. The results showed that the risk quotient for PAHs (RQPAHs) was ≥1. In turn, the summed RQ for all PACs (∑RQmixture) ranged from 1 to 30, but did not exceed the maximum allowable threshold; thus, the risks posed to benthic species were moderate for all sediment samples.

Occurrence of 3-nitrobenzanthrone and other powerful mutagenic polycyclic aromatic compounds in living organisms: polychaetes.

In this work we report the occurrence of powerful mutagenic 3-nitrobenzanthrone (3-NBA), in addition to 18 polycyclic aromatic hydrocarbons (PAHs), 6 oxygenated PAHs and 27 nitrated PAHs in polychaete worms. Benzanthrone (BA), another important mutagenic polycyclic aromatic compound (PAC) also was detected in the samples. Polychaete annelids have great ecological relevance, being widely distributed in different environmental conditions, from intertidal zones up to seven thousand feet deep areas. They are abundantly found in both contaminated and uncontaminated areas and, therefore, used as indicators of the pollution status of a given area. As we know, so far, most of these PACs has not been previously reported in living organisms before. The 3-NBA concentrations determined in this study were within 0.11-5.18 µg g-1. Other relevant PACs such as PAHs, quinones and nitro-PAHs were found in maximum concentrations at 0.013 µg g-1 (coronene) to 11.1 µg g-1 (benzo[k]fluoranthene), 0.823 µg g-1 (9,10-phenenthrenequinone) to 12.1 µg g-1 (1,4-benzoquinone) and 0.434 (1-nitronaphthalene) µg g-1 to 19.2 µg g-1 (6-nitrobenzo[a]pyrene), respectively. Principal component analysis (PCA), ternary correlations and diagnostic ratios were employed in order to propose probable sources for PACs. Although statistical analysis preliminarily has indicated both pyrogenic and petrogenic contributions, petrogenic sources were predominant reflecting the impacts of petroleum exploration and intensive traffic of boats in the study area.

Microwave-assisted digestion using diluted HNO3 and H2O2 for macro and microelements determination in guarana samples by ICP OES.

A microwave-assisted digestion procedure using diluted HNO3 and H2O2 was developed for multi-element determination in guarana samples by ICP OES. Optimization step was performed employing a mixture design with pseudocomponents using HNO3, H2O2 and H2O. The analytical signal of each element, residual acidity and residual carbon content were optimized simultaneously using the desirability function. The best condition for digestion of a 250 mg sample mass resulted from a mixture constituted by 1.0 mL of HNO3, 3.0 mL of H2O2 and 6.0 mL of H2O. This condition allowed final digests with residual acidity and residual carbon content of 0.4 mol L-1 and 6.5%, respectively. The method was validated and applied for the determination of K, Ca, Mg, S, P, Cu, Fe, Mn and Zn in 72 guarana seed samples from Bahia state. This work presents unpublished results about the mineral composition of guarana seed samples produced in Bahia state, Brazil.

Pesticides in fine airborne particles: from a green analysis method to atmospheric characterization and risk assessment.

The intensive use of pesticides such as herbicides, insecticides, fungicides and acaricides has been lead to ubiquitous contamination, being present not only in soils, water bodies and/or crops, but also in the atmosphere. Considering the massive amount of pesticides employed globally, together to their persistence, this may be an important concern regarding air quality and human health worldwide. In the present study we developed a green sensitive sample preparation method for determination of nine organophosphates, two pyrethroids, one carbamate, and one strobirulin in PM2.5 collected in a tropical coastal area in the Southern Hemisphere for the first time. Extraction of PM2.5 sample masses, as low as 206 µg, were performed in a miniaturized device using 500 µL of a mixture containing 18% acetonitrile in dichloromethane followed by sonication for 23 minutes and injection into GC-MS. A total of 12 pesticides were identified and quantified successfully, among them, eight banned pesticides. A risk assessment exposure and cancer risk for possible carcinogenic pesticides (bifenthrin, malathion, parathion and permethrin) were performed for exposure of adults, children and infants. Hazard Quotient and cumulative exposure for organophosphate and pyrethroid pesticides were less than 1, showing that cumulative risk is within acceptable range.