Sonophotocatalytic Degradation of Chitosan in the Presence of Fe(III)/H2O2 System

The degradation of chitosan by means of ultrasound irradiation and its combination with homogeneous photocatalysis (photo-Fenton) was investigated. Emphasis was given on the effect of additive on degradation rate constants. 24 kHz of ultrasound irradiation was provided by a sonicator, while an ultraviolet source of 16 W was used for UV irradiation. To increase the efficiency of degradation process, degradation system was combined with Fe(III) (2.5 × 10⁻⁴mol/L) and H₂O₂ (0.020–0.118 mol/L) in the presence of UV irradiation and the rate of degradation process change from 1.873 × 10⁻⁹−6.083 × 10⁻⁹ mol^1.7 L s⁻¹. Photo-Fenton process led to complete chitosan degradation in 60 min with the rate increasing with increasing catalyst loading. Sonophotocatalysis in the presence of Fe(III)/H₂O₂ was always faster than the respective individual processes. A synergistic effect between ultrasound and ultraviolet irradiation in the presence of Fenton reagent was calculated. The degraded chitosans were characterized by X-ray diffraction (XRD), gel permeation chromatography (GPC) and Fourier transform infrared (FT-IR) spectroscopy and average molecular weight of ultrasonicated chitosan was determined by measurements of intrinsic viscosity of samples. The results show that the total degree of deacetylation (DD) of chitosan change, partially after degradation and the decrease of molecular weight led to transformation of crystal structure. A negative order for the dependence of the reaction rate on total molar concentration of chitosan solution within the degradation process was suggested. Results of this study indicate that the presence of catalyst in the reaction medium can be utilized to reduce molecular weight of chitosan while maintaining the power of irradiated ultrasound and degree of deacetylation.     

Eriophorum angustifolium and Lolium perenne metabolic adaptations to metals- and metalloids-induced anomalies in the vicinity of a chemical industrial complex

As plants constitute the foundation of the food chain, concerns have been raised about the possibility of toxic concentrations of metals and metalloids being transported from plants to the higher food chain strata. In this perspective, the use of important phytotoxicity endpoints may be of utmost significance in assessing the hazardous nature of metals and metalloids and also in developing ecological soil screening levels. The current study aimed to investigate the role of glutathione (GSH) and its associated enzymes in the metabolic adaptation of two grass species namely Eriophorum angustifolium Honck. and Lolium perenne L. to metals and metalloids stress in the vicinity of a chemical industrial complex (Estarreja, Portugal). Soil and plant samples were collected from contaminated (C) and non-contaminated (reference, R) sites, respectively, near and away from the Estarreja Chemical Complex, Portugal. Soils (from 0 to 10 and 10 to 20 cm depths) were analyzed for pH, organic carbon, and metals and metalloids concentrations. Plant samples were processed fresh for physiological and biochemical estimations, while oven-dried plant samples were used for metals and metalloids determinations following standard methodologies. Both soils and plants from the industrial area exhibited differential concentrations of major metals and metalloids including As, Cu, Hg, Pb, and Zn. In particular, L. perenne shoot displayed significantly higher and lower concentrations of Pb and As, respectively at contaminated site (vs. E. angustifolium). Irrespective of sites, L. perenne shoot exhibited significantly higher total GSH pool, oxidized glutathione (GSSG) and oxidized protein (vs. E. angustifolium). Additionally, severe damages to photosynthetic pigments, proteins, cellular membrane integrity (in terms of electrolyte leakage), and lipid peroxidation were also perceptible in L. perenne shoot. Contrarily, irrespective of the sites, activities of catalase and GSH-regenerating enzyme, GSH reductase, and GSH-metabolizing enzymes such as GSH peroxidase and GSH sulfotransferase were significantly higher in shoot of E. angustifolium. Despite the higher total GSH content, L. perenne is vulnerable to multi-metals-induced stress in comparison to E. angustifolium as depicted by increased GSH- and protein oxidation, low reactive oxygen radical-processing potential (exhibited in terms of low catalase activity) and poor GSH pool utilization efficiency (in terms of lower GSH-associated enzymes activities). The outcome of the present study may be significant for understanding vital GSH-mediated metals and metalloids tolerance mechanisms in plants as well as their unsuitability for animal consumption due to higher metals and metalloids burdens.     

Phenological development stages variation versus mercury tolerance,accumulation, and allocation in salt marsh macrophytes <Emphasis Type="Italic">Triglochin maritima</Emphasis> and <Emphasis Type="Italic">Scirpus maritimus</Emphasis> prevalent in Ria de Aveiro coastal lagoon (Portugal)

Efficient and sustainable management of rapidly mounting environmental issues has been the focus of current intensive research. The present study aimed to investigate the impact of plant phenological development stage variation on mercury (Hg) tolerance, accumulation, and allocation in two salt marsh macrophytes Triglochin maritima and Scirpus maritimus prevalent in historically Hg-contaminated Ria de Aveiro coastal lagoon (Portugal). Both plant samples and the sediments vegetated by monospecific stands of T. maritima and S. maritimus were collected from reference (R) and sites with moderate (M) and high (H) Hg contamination in Laranjo bay within Ria de Aveiro lagoon. Hg tolerance, uptake, and allocation in T. maritima and S. maritimus, physico-chemical traits (pH, redox potential, and organic matter content) and Hg concentrations in sediments vegetated by these species were impacted differentially by phenological development stages variation irrespective of the Hg contamination level. In T. maritima, Hg concentration increased with increase in Hg contamination gradient where root displayed significantly higher Hg followed by rhizome and leaf maximally at H. However, in S. maritimus, the highest Hg concentration was perceptible in rhizome followed by root maximally at M. Between the two studied plant species, S. maritimus displayed higher Hg tolerance index (depicted by higher plant dry mass allocated to reproductive stage) and higher available Hg at M (during all growth stages) and H (during senescent stage) when compared to T. maritimus. Both plant species proved to be Hg excluder (low root/rhizome–leaf Hg translocation). Additionally, T. maritima also acted as Hg stabilizer while, S. maritimus as Hg accumulator. It can be inferred from the study that (a) the plant phenological development stage variations significantly influenced plant Hg sensitivity by impacting sediment chemistry, plant growth (in terms of plant dry mass), Hg accumulation, and its subsequent allocation capacity, contingent to Hg contamination gradient; (b) S. maritimus accumulated higher Hg but restricted its translocation to above-ground part using exclusion process at both M and H due to its accelerated growth during Hg-tolerant reproductive/metabolically active phenological development stage greater than its counterpart T. maritima; and (c) the studied salt marsh plants although hailed from the same C3 and monocot group did not necessarily display similar phenotypic plasticity and behavior towards Hg-contaminated scenario during their life cycle.     

Effects of three biochars on copper immobilization and soil microbial communities in a metal-contaminated soil using a metallophyte and two agricultural plants

Environmental Geochemistry and Health - Biochar (BC) is a porous, carbonaceous material produced by slow pyrolysis of biomass under oxygen-limited conditions. BC production has been attracting...     

Antioxidant enzymes and compounds complement each other during arsenic detoxification in shoots of Isatis cappadocica Desv.

Isatis cappadocica has been reported to be an arsenic (As) hyperaccumulator. Antioxidant enzymes and compounds have been proposed to play an important role in the detoxification and tolerance of As. In the present study, As-induced oxidative stress and antioxidant responses were investigated on I. cappadocica grown hydroponically in response to application of arsenate (0–1200?μmol). As accumulation increased with an increase in arsenate concentration in the medium. Along with a significant increase in arsenate concentration, a build up in hydrogen peroxide, indicators of oxidative stress, was observed. The activity of superoxide dismutase and peroxidase was induced after arsenate treatment, reached a maximal value at 800?μmol arsenate and then declined at the highest arsenate treatment. Glutathione reductase activity and contents of non-enzymatic antioxidants (carotenoids, flavonoids and anthocyanins) increased significantly as arsenate concentration augmented. These results indicated that high efficient antioxidant system may play significant roles in As detoxification and improve I. cappadocica tolerance against As toxicity.     

Microwave Assisted Synthesis of Urethane Modified Polyesteramide Coatings from Jatropha Seed Oil

In this study, we have developed urethane modified polyesteramide (UPEA) resin by the condensation polymerization reaction of N,N-bis (2-hydroxy ethyl) jatropha oil fatty amide (HEJA) and itaconic acid to form polyesteramide (PEA). The latter was further reacted with different percentages (16–22%) of toluylene 2,4-diisocyanate (TDI) to prepare UPEA. The structural elucidation of HEJA, PEA, UPEA was carried out by FT-IR, ¹H-NMR and ¹³C-NMR spectroscopic techniques. The coating was made on mild steel strips. The physico-chemical and physico-mechanical analyses were carried out by standard laboratory methods. The thermal stability of polymer was studied by thermogravimetric analysis. Thermal analyses shows that these coatings can be used safely up to 230 °C. The corrosion protective behavior of UPEA coatings was investigated in acid, alkali, water and xylene. All the coatings exhibited good chemical resistance performance in acid, alkali, saline and organic solvents, while the resin UPEA 20 showed the best performance.     

A multivariable approach for estimation of vapor cloud explosion frequencies for independent congested spaces to be used in occupied building risk assessment

API Recommended Practice 752 is one of the most referenced practices for evaluating vapor cloud explosion (VCE) impacts to site occupied buildings. This reference introduces generic VCE frequencies for different types of process units that are based on VCE incidents database. Although these reported VCE frequencies are not capable of illustrating all parameters that affect explosion likelihood, they are widely used in risk analysis studies and software packages. This paper delineates the structure of a more realistic method for estimation of local VCE frequencies for independent congested spaces or units as a function of process, site, and meteorological variables. Compared to traditional methods for VCE frequency estimation, the new proposed approach is supported by an obviously more populated and precisely categorized database of leakage frequencies and features a multi-variable functionality of process/plant conditions. Contrary to previous procedures that aimed at finding the frequency of occurrence for a single VCE incident, this proposed methodology characterizes each congested space with a local VCE frequency. This frequency is an integration of the frequencies pertaining to VCE's that are likely to be initiated by each congested space. This new VCE frequency can also be used to determine the level of explosion hazard in each unit and in risk matrix analysis.     

Extraction and characterization of chitin,chitosan, and protein hydrolysate from the invasive Pacific blue crab,Portunus segnis (Forskål, 1775) having potential biological activities

Environmental Science and Pollution Research - The diversity of marine biomasses is a set of exploitable and renewable resources with application in several sectors. In this context, a co-culture...     

A risk-based decision making approach to determine fireproofing requirements against jet fires

API Publication 2218 is one of the most referred practices for fireproofing of onshore structural supports. Despite the extensive citation, it solely considers the effects of pool fire and rarely addresses jet fire outcomes. This absence of an explicit approach is common among all the other major references. Therefore, the basic objective of this paper is to introduce a new approach for determination of the necessity for fireproofing of structural supports against jet fires. For this purpose, the flame geometry and duration of jet fires are simulated for different leak sizes in identified fire potential sources. Then, following a worst-case analysis, those structures that may be impinged by long enough flames are screened out and then characterized by maximum impingement duration for fireproofing purpose. Moreover, each structure is assigned by a failure rate to estimate the degree of vulnerability through a detailed risk assessment. In this regard a new explanatory term called Structure Failure Rate (SFR) is introduced. This approach also enables researchers to quantify the effect of other protective systems (fire and gas detection, emergency shut-down, depressurization and firewalls) on the level of required fireproofing.