Functional group influences on the reactive azo dye decolorization performance by electrochemical oxidation and electro-Fenton technologies

Electrochemical water treatment technologies are highly promising to achieve complete decolorization of dyebath effluents, as demonstrated by several studies reported in the literature. However, these works are focused on the treatment of one model pollutant and generalize the performances of the processes which are not transposable since they depend on the pollutant treated. Thus, in the present study, we evaluate, for the first time, the influence of different functional groups that modify the dye structure on the electrochemical process decolorization performance. The textile azo dyes Reactive Orange 16, Reactive Violet 4, Reactive Red 228, and Reactive Black 5 have been selected because they present the same molecular basis structure with different functional groups. The results demonstrate that the functional groups that reduce the nucleophilicity of the pollutant hinder the electrophilic attack of electrogenerated hydroxyl radical. Thereby, the overall decolorization efficiency is consequently reduced as well as the decolorization rate. Moreover, the presence of an additional chromophore azo bond in the molecule enhances the recalcitrant character of the azo dyes as pollutants. The formation of a larger and more stable conjugated π system increases the activation energy required for the electrophyilic attack of ^?OH, affecting the performance of electrochemical technologies on effluent decolorization.     

Novel two-step vapor-phase synthesis of UV–Vis light active Fe2O3/WO3 nanocomposites for phenol degradation

Supported Fe₂O₃/WO₃ nanocomposites were fabricated by an original vapor phase approach, involving the chemical vapor deposition (CVD) of Fe₂O₃ on Ti sheets and the subsequent radio frequency (RF)-sputtering of WO₃. Particular attention was dedicated to the control of the W/Fe ratio, in order to tailor the composition of the resulting materials. The target systems were analyzed by the joint use of complementary techniques, that is, X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), energy dispersive X-ray spectroscopy (EDXS), X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), and optical absorption spectroscopy. The results showed the uniform decoration of α-Fe₂O₃ (hematite) globular particles by tiny WO₃ aggregates, whose content could be controlled by modulations of the sole sputtering time. The photocatalytic degradation of phenol in the liquid phase was selected as a test reaction for a preliminary investigation of the system behavior in wastewater treatment applications. The system activity under both UV and Vis light illumination may open doors for further material optimization in view of real-world end-uses.

     

Remobilization of trace elements by forest fire in Patagonia,Chile

Temporal changes in the amounts of trace elements (As, Co, Cu, Mn, Ni, Pb, and Zn) and their correlations with temporal changes in charcoal abundance in age-dated sediments collected from Lake Thompson in Patagonia, Chile, attest to the substantial pyrogenic remobilization of contaminants that occurred in Patagonia during the mid-1900s. This remobilization was concurrent with the extensive slash and burn period in the region during that period. The changes in concentrations of Co, Cu, and Ni in relation to charcoal abundance in the lacustrine sediments over time were small compared to those of As, Mn, Pb, and Zn. However, the relatively low enrichment factors of all those trace elements, normalized to Fe, indicate that they were predominantly derived from local, natural sources impacted by fires rather than industrial sources. The primarily local source of Pb in the sediments was corroborated by the temporal consistency of its isotopic ratios (²⁰⁶Pb/²⁰⁷Pb:²⁰⁸Pb/²⁰⁶Pb), which were similar to previously reported values for natural lead in Central and Southern Chile. However, the pyrogenic remobilization of both natural and industrial trace elements by forest fires in Chile and elsewhere is expected to rise as a consequence of climate change, which is projected to increase both the frequency and intensity of forest fires on a global scale.     

Bioaccumulation of butyltins and liver damage in the demersal fish Cathorops spixii (Siluriformes,Ariidae)

The toxicity of butyltin compounds (BTs), mainly tributyltin (TBT), has been reported in different organisms. However, such an analysis in fish after field exposure with reference to the related biomarkers has not been commonly observed in the literature. This study presents the uptake of BTs in the liver of a neotropical marine catfish Cathorops spixii in Paranagua Bay, an important estuarine system located in southern Brazil. Two different areas, close to and distant from the harbor, were used for chemical analysis evaluation of hepatotoxicity through genetic, enzymatic, and histopathological biomarkers. The presence of polycyclic aromatic hydrocarbons in bile was also considered as a biomarker. The results showed a significant relationship between TBT levels and the inhibition of biotransformation enzymes and high occurrence of melanomacrophages in fish collected close to the harbor site. These effects were linked to the absence of TBT metabolites in the liver. In the second site, the presence of DBT was associated with an increase in EROD and GST activity. The larger amount of DNA damage as well as the highest oxidative stress was noted in fish from the less TBT-polluted area, where DBT and bile PAHs occurred. These findings showed different impact levels due to or increased by the chronic exposure of biota to BTs.     

Source identification of inorganic airborne particle fraction (PM10) at ultratrace levels by means of INAA short irradiation

Many studies have focused their attention on the determination of elements of toxicological and environmental interest in atmospheric particulate matter using analytical techniques requiring chemical treatments. The instrumental nuclear activation analysis technique allows achieving high sensitivity, good precision, and excellent limit of detection without pretreatment, also considering the problems related to the radioisotope characteristics (e.g., half-life time, interfering reactions, spectral interferences). In this paper, elements such as Al, As, Br, Cl, Cu, I, La, Mg, Mn, Na, Sb, Si, Ti, and V are studied in atmospheric PM₁₀ sampled in downtown Rome: The relative radionuclides after activation of the sample are characterized by very short (ranging from 2.24 to 37.2 min) and short (ranging from 2.58 h to 2.70 days) half-lives. Furthermore, As, Br, La, Mn, and Sb were also determined for evaluating the aerosol characteristics. The results, elaborated considering the matrix effects and the interfering reaction contribution to the radioisotope formation (e.g., ²⁸Al generated by both (n,γ) reaction from ²⁷Al and (n,p) reaction from ²⁸Si), show interesting values of As (0.3–6.1 ng m^?3), Cu (22–313 ng m^?3), Mn (17–125 ng m^?3), V (7–63 ng m^?3), higher than those determined in an area not influenced by autovehicular traffic, and significant levels of I (1–11 ng m^?3) and Ti (25–659 ng m^?3) in Rome PM₁₀. The other elements show a pattern similar to the very few data present in the literature. It should be underlined the good correlation (r ²) of Al vs. Mg (0.915) and Al vs. La (0.726), indicating a same sources for these species as well as Br–Sb showing a little lower correlation (0.623). This last hypothesis is confirmed by the study of the enrichment factors: Sb and Br may be attributed to anthropogenic sources; Cu, Cl, and I show a mixed origin (natural and anthropogenic), whereas Al, Si, Ti, Mn, Na, Mg, and As are of crustal origin. For having more information, a statistical approach based on the principal component analysis and the canonical discriminant analysis has been performed: All the samples (except one) are grouped in a cluster, and elements such as As, Br, Cu, I, La, Mn, Sb, Ti, and V are highly correlated, whereas Na and Cl and Mg and Al assemble in two different clusters. Finally, a comparison with other similar studies is reported showing interesting values for Al, As, Mg, Mn, and Ti.     

Changes in the microbial communities during co-composting of digestates

Anaerobic digestion is a waste treatment method which is of increasing interest worldwide. At the end of the process, a digestate remains, which can gain added value by being composted. A study was conducted in order to investigate microbial community dynamics during the composting process of a mixture of anaerobic digestate (derived from the anaerobic digestion of municipal food waste), green wastes and a screened compost (green waste/kitchen waste compost), using the COMPOCHIP microarray. The composting process showed a typical temperature development, and the highest degradation rates occurred during the first 14 days of composting, as seen from the elevated CO₂ content in the exhaust air. With an exception of elevated nitrite and nitrate levels in the day 34 samples, physical–chemical parameters for all compost samples collected during the 63 day process indicated typical composting conditions. The microbial communities changed over the 63 days of composting. According to principal component analysis of the COMPOCHIP microarray results, compost samples from the start of the experiment were found to cluster most closely with the digestate and screened compost samples. The green waste samples were found to group separately. All starting materials investigated were found to yield fewer and lower signals when compared to the samples collected during the composting experiment.     

Assessment of compost quality for its environmentally safe use by means of an ecotoxicological test on a soil organism

A research project was carried out to evaluate toxicological effects of compost addition to agricultural soil using the earthworm Eisenia foetida (Annellida) as a representative organism of the soil fauna. Moreover, the correlation between compost biochemical stabilization and toxicity at different phases of the composting process was assessed. Samples were collected from three composting plants at three different maturation levels (beginning of the composting process, intermediate compost after bio-oxidation, and mature refined compost). Two tests were performed: a standard chronic solid-phase test and an acute solid-phase test (developed originally by the authors). In the first test, the measured end-points were mortality, growth and reproduction; while in the second test earthworms’ behavior was evaluated. The chosen compost concentrations in soil ranged from 2.5 to 100 %, with the aim of obtaining the toxicological parameters (LC50) and to mimic real agricultural dosages for the lower concentrations. Results indicated an increase in compost toxicity with greater compost concentrations; in particular, agricultural compost dosage below 10 % showed no toxicity. Moreover, toxicity did not decrease during composting; intermediate compost showed the highest LC50 values. As a consequence, no correlation was ascertained between the results of ecotoxicological analysis and waste biochemical stability parameters during the composting process.     

Performance of a Semi-Industrial Scale Gasification Process for the Destruction of Polychlorinated Biphenyls

Abstract

A semi-industrial scale test was conducted to thermally treat mixtures of spent oil and askarels at a concentration of 50,000 ppm and 100,000 ppm of polychlorinated biphenyls (PCBs) under a reductive atmosphere. In average, the dry-basis composition of the synthesis gas (syngas) obtained from the gasification process was: hydrogen 46%, CO 34%, CO₂ 18%, and CH₄ 0.8%. PCBs, polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans (PCDDs/PCDFs) in the gas stream were analyzed by high-resolution gas chromatography (GC)-mass spec-trometry. The coplanar PCBs congeners 77, 105, 118, 156/157, and 167 were detected in the syngas at concentrations <2 ×10^?7 mg/m³ (at 298 K, 1 atm, dry basis, 7% O₂). The chlorine released in the destruction of the PCBs was transformed to hydrogen chloride and separated from the gas by an alkaline wet scrubber. The concentration of PCBs in the water leaving the scrubber was below the detection limit of 0.002 mg/L, whereas the destruction and removal efficiency was >99.9999% for both tests conducted. The concentration of PCDDs/PCDFs in the syngas were 8.1 ×10^?6 ng-toxic equivalent (TEQ)/m³ and 7.1 × 10^?6 ng-TEQ/m³ (at 298 K, 1 atm, dry basis, 7% O₂) for the tests at 50,000 ppm and 100,000 ppm PCBs, respectively. The only PCDD/F congener detected in the gas was the octachloro-dibenzo-p-dioxin, which has a toxic equivalent factor of 0.001. The results obtained for other pollutants (e.g., metals and particulate matter) meet the maximum allowed emission limits according to Mexican, U.S., and European regulations for the thermal treatment of hazardous waste (excluding CO, which is a major component of the syngas, and total hydrocarbons, which mainly represent the presence of CH₄).     

Method of median semi-variance for the analysis of left-censored data: Comparison with other techniques using environmental data

In environmental monitoring, variables with analytically non-detected values are commonly encountered. For the statistical evaluation of these data, most of the methods that produce a less biased performance require specific computer programs. In this paper, a statistical method based on the median semi-variance (SemiV) is proposed to estimate the position and spread statistics in a dataset with single left-censoring. The performances of the SemiV method and 12 other statistical methods are evaluated using real and complete datasets. The performances of all the methods are influenced by the percentage of censored data. In general, the simple substitution and deletion methods showed biased performance, with exceptions for L/2, Inter and L/√2 methods that can be used with caution under specific conditions. In general, the SemiV method and other parametric methods showed similar performances and were less biased than other methods. The SemiV method is a simple and accurate procedure that can be used in the analysis of datasets with less than 50% of left-censored data.     

Microalgae biosynthesis of silver nanoparticles for application in the control of agricultural pathogens

The occurrence of diseases in cultivars has caused significant losses in global food production. The advancement of nanobiotechnology makes it possible to obtain new products to be used in the control of pathogens in cultivars. Silver nanoparticles can be synthesized by microalgae and are widely known for their antimicrobial activity. In addition, the biomass produced in microalgal culture for the biosynthesis of the nanoparticles also demonstrates antimicrobial properties, as it can increase the antibacterial and antifungal potential of the silver nanoparticles. In this context, this article addresses the use of microalgae to biosynthesize silver nanoparticles simultaneously with biomass production. In addition, we demonstrate the antimicrobial potential of these nanomaterials, as well as of the microalgal biomass produced in biosynthesis, to use in the control of pathogens in agriculture.