Nanoporous activated carbon fluidized bed catalytic oxidations of aqueous o, p and m-cresols: kinetic and thermodynamic studies

Nanoporous activated carbon prepared from rice husk through precarbonisation at 400 °C and phosphoric acid activation at 800 °C was used as fluidized bed in Fenton oxidation of the o, p and m-cresols in aqueous solution. The efficiencies of homogeneous Fenton oxidation, fluidized Fenton oxidation and aerobic biological oxidation systems for the removal of o, p and m-cresols in aqueous solution have been compared. The kinetic constants and the thermodynamic parameters for the homogeneous Fenton, heterogeneous Fenton and aerobic biological oxidations of o, p and m-cresols in synthetic wastewater were determined. The degradation of cresols in synthetic wastewater was confirmed using FT-IR, ¹H-NMR and UV–visible spectroscopy.     

Genotoxic effect of ciprofloxacin during photolytic decomposition monitored by the in vitro micronucleus test (MNvit) in HepG2 cells

Purpose

Ciprofloxacin (CIP), a broad-spectrum, second-generation fluoroquinolone, has frequently been found in hospital wastewaters and effluents of sewage treatment plants. CIP is scarcely biodegradable, has toxic effects on microorganisms and is photosensitive. The aim of this study was to assess the genotoxic potential of CIP in human HepG2 liver cells during photolysis.

Methods

Photolysis of CIP was performed in aqueous solution by irradiation with an Hg lamp, and transformation products were monitored by HPLC-MS/MS and by the determination of dissolved organic carbon (DOC). The cytotoxicity and genotoxicity of CIP and of the irradiated samples were determined after 24?h of exposure using the WST-1 assay and the in vitro micronucleus (MN) test in HepG2 cells.

Results

The concentration of CIP decreased during photolysis, whereas the content of DOC remained unchanged. CIP and its transformation products were not cytotoxic towards HepG2 cells. A concentration-dependent increase of MN frequencies was observed for the parent compound CIP (lowest observed effect level, 1.2???mol?L^?1). Furthermore, CIP and the irradiated samples were found to be genotoxic with a significant increase relative to the parent compound after 32?min (P?P?Conclusions Photolytic decomposition of aqueous CIP leads to genotoxic transformation products. This proves that irradiated samples of CIP are able to exert heritable genotoxic effects on human liver cells in vitro. Therefore, photolysis as a technique for wastewater treatment needs to be evaluated in detail in further studies, not only for CIP but in general.     

Superior photodecomposition of pyrene by metal ion-loaded TiO₂ catalyst under UV light irradiation

BACKGROUND: The photocatalytic degradation of pyrene under UV (125 W Hg-Arc, 10.4 mW/cm2) irradiation of TiO2 aqueous suspension has been found to be highly improved with the dissolved transition metal ions like Cu2+, Fe3+, Ag+, and Au3+, etc. As the reduction potential of these metals lies below the conduction band (CB) position (?0.1 eV) of TiO2, the photoexcited electron transfer occurs more readily and reduces electron–hole recombination rate. Therefore, it has a beneficial influence on the photocatalytic ability of TiO2 because of rapid Fermi energy equilibrium between the CB of TiO2 and its surface adsorbed metal ions. RESULTS AND DISCUSSION: The Fermi level is referred to as the electrochemical potential and plays an important role in the band theory of solids. When metal and semiconductor are in contact, electron migration from photoirradiated semiconductor to the deposited metal occurs at the interface until two Fermi levels equilibrate and enhanced the photocatalytic activity of semiconductor photocatalyst. Ni2+ having more negative reduction potential (?0.25 eV) than the CB of TiO2 imparts negligible co-catalytic activity to TiO2 photoreaction. It also revealed that loading of Au3+ ions displayed higher degradation rate of pyrene than Au photodeposition. Furthermore, when the amount of dissolved Fe+3 and Au3+ ions gradually increases from 0.1 to 2 wt.%, the pyrene photodecomposition rate also become faster.     

Susceptibility of epigeic earthworm Eisenia fetida to agricultural application of six insecticides

Ecotoxicological risks of agricultural application of six insecticides to soil organisms were evaluated by acute toxicity tests under laboratory condition following OECD guidelines using the epigeic earthworm Eisenia fetida as the test organism. The organochlorine insecticide endosulfan (LC₅₀ - 0.002 mg kg⁻¹) and the carbamate insecticides aldicarb (LC₅₀ - 9.42 mg kg⁻¹) and carbaryl (LC₅₀ - 14.81 mg kg⁻¹) were found ecologically most dangerous because LC₅₀ values of these insecticides were lower than the respective recommended agricultural dose (RAD). Although E. fetida was found highly susceptible to the pyrethroid insecticide cypermethrin (LC₅₀ - 0.054 mg kg⁻¹), the value was higher than its RAD. The organophosphate insecticides chlorpyrifos (LC₅₀ - 28.58 mg kg⁻¹), and monocrotophos (LC₅₀ - 39.75 mg kg⁻¹) were found less toxic and ecologically safe because the LC₅₀ values were much higher than their respective RAD.     

Epibrassinolide ameliorates Cr (VI) stress via influencing the levels of indole-3-acetic acid, abscisic acid, polyamines and antioxidant system of radish seedlings

The present investigation determined the effects of epibrassinolide (EBL) on the levels of indole-3-acetic acid (IAA), abscisic acid (ABA), and polyamine (PA) and antioxidant potential of 7-d old Raphanus sativus L. cv. ‘Pusa chetki’ seedlings grown under Cr (VI) metal stress. Reduced titers of free (0.767 μg g⁻¹ FW) and bound (0.545 μg g⁻¹ FW) IAA in Cr (VI) stressed seedlings were observed over untreated control. Supplementations of EBL to Cr (VI) stressed seedlings were able to enhance both free (2.14-5.68 μg g⁻¹ FW) and bound IAA (2.45-7.78 μg g⁻¹ FW) concentrations in comparison to Cr (VI) metal treatment alone. Significant rise in free (13.49 μg g⁻¹ FW) and bound (12.17 μg g⁻¹ FW) ABA contents were noticed for Cr (VI) stressed seedlings when compared to untreated control. No significant increase in ABA contents were recorded for Cr (VI) stressed seedlings upon supplementation with EBL over Cr (VI) treatment alone. A significant increase in Put (18.40 μg g⁻¹ FW) and Cad (9.08 μg g⁻¹ FW) contents were found for 10⁻⁹ M EBL plus Cr (VI) metal treatments when compared to Cr (VI) treatment alone. Spermidine (Spd) contents were found to decline significantly for EBL treatment alone or when supplemented with Cr (VI) treatments over untreated controls and Cr (VI) treatment alone. Antioxidant levels were found to enhance, with glutathione (57.98 mg g⁻¹ FW), proline (4.97 mg g⁻¹ FW), glycinebetaine (39.01 μmol mL⁻¹), ascorbic acid (3.17 mg g⁻¹ FW) and phytochelatins (65.69 μmol g⁻¹ FW) contents noted for EBL supplemented to Cr (VI) metal solution over Cr (VI) treatment alone. Reduced activities of guaiacol peroxidase (0.391 U mg⁻¹ protein) and catalase (0.221 U mg⁻¹ protein) and enhanced activities of glutathione reductase (7.14 U mg⁻¹ protein), superoxide dismutase (15.20 U mg⁻¹ protein) and ascorbate peroxidase (4.31 U mg⁻¹ protein) were observed in seedlings treated with EBL plus Cr (VI) over Cr metal treatment alone. Reduced MDA (2.55 μmol g⁻¹ FW) and H₂O₂ (33.24 μmol g⁻¹ FW) contents were recorded for 10⁻⁹ M EBL supplemented to Cr (VI) stress over Cr (VI) treatment alone. Enhancement in free radical scavenging potential as indicated by higher values of 1,1-diphenylpicrylhydrazyl, deoxyribose and reducing power activity assays, and increased levels of phenols and soluble sugars also showed significant influence of EBL in alleviating Cr (VI) stress in radish seedlings.     

Uptake and translocation of metals in Spinacia oleracea L. grown on tannery sludge-amended and contaminated soils: effect on lipid peroxidation, morpho-anatomical changes and antioxidants

The plants of Spinacia oleracea L. grown on contaminated soil (CS) and different amendments of tannery sludge (TS) have shown high accumulation of metals in its edible part. The accumulation of toxic metal (Cr) in the leaves of the plants grown on CS was recorded as 40.67 microgg(-1)dw. However, the leaves of the plants grown on 100% TS have accumulated about two times (70.80 microgg(-1)dw) higher Cr than the 10% TS (31.21 microgg(-1)dw). Among growth parameters, the root length was more affected at 90 d than the shoot length, number of leaves and leaf area. The study of scanning electron micrographs showed 29.31% increase in stomatal length in the leaves of the plants grown on CS as compared to garden soil (GS), which served as control, however it decreased in the plants grown on higher amendments of TS. The decrease in MDA content at initial period of exposure and lower amendment was recorded in the leaves, whereas, significant increase (>10% TS onward) was observed with increase in tannery sludge ratio at 90 d as compared to GS. A coordinated increase in all the studied antioxidants (cysteine, non-protein thiol, ascorbic acid, carotenoid contents) was found up to 75 d of growth. At 90 d, most of the antioxidant decreased as compared to 75 d causing oxidative stress as evidenced by increased level of lipid peroxidation and decreased chlorophyll and protein contents. Maximum increase of 181.43% in MDA content and maximum decrease of 53.69% in total chlorophyll content was recorded in the leaves of the plants grown on 100% TS after 90 d of growth. The plants grown on CS have shown an increase in shoot length, number of leaves, leaf area, photosynthetic pigments and protein contents and in all the studied antioxidants. Thus, these plants are able to combat stress involving defense mechanism, resulting in healthy growth of the plants. The results are well coordinated as there is no change in the MDA content as compared to the plants grown on GS. In view of high Cr accumulation in edible part of S. oleracea grown on CS after irrigation with tap water, it is not advisable to use these plants for edible purposes. Summing up, it is recommended that the level of metals in the edible part should be checked instead of healthy growth as deciding parameter for consumption. It is demonstrated through this study that metal enriched plants have detoxification mechanism and grow well on organic matter enriched contaminated soil.     

Treatment of phenolic wastewater by horseradish peroxidase immobilized by bioaffinity layering

Horseradish peroxidase was immobilized by bioaffinity layering and used for the treatment of wastewater containing p-chlorophenol. For this purpose, lectin Concanavalin A was bound to Sephadex beads. The glycoenzyme peroxidase was layered upon this Con A layer. Subsequently, alternate layers of the enzyme and Con A were applied. The most efficient design consisted of three layers of Con A and peroxidase each. This immobilized enzyme preparation retained 80% of the activity of the free peroxidase used for immobilization. PEG at the concentration of 0.1 mg ml(-1) was found to prevent enzyme inactivation by the products, although it increased the process time. Thus 60 U ml(-1) of enzyme completely converted the p-chlorophenol (into products) in 4 min in the absence of PEG. On the other hand, only 0.05 U ml(-1) of enzyme was required for this purpose in the presence of PEG but the process required 60 min. Peroxidase converts phenol molecules into free radicals. These free radicals then polymerize and get precipitated. As a further means of minimizing exposure of the enzyme to free radicals and enhancing the reusability, it was decided to remove the enzyme from reaction medium after 10 min. With this strategy, the bioaffinity layered peroxidase preparation could be reused five times without any loss of activity.     

Controlled release of thiram fungicide from starch-based hydrogels

In order to make the judicious use of thiram fungicide and to exploit the potential of agri-polymers, we have developed the starch- poly(acrylamide) and starch-poly(acrylic acid) based agrichemical delivery system (hydrogels) for its controlled and sustained release. Polymeric networks have been prepared by using N,N'-methylenebisacrylamide (N,N-MBAAm) as crosslinker and ammonium persulfate (APS) as initiator and characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and swelling studies. Release dynamics of thiram fungicide from polymeric matrices has been studied for the evaluation of the diffusion mechanism and diffusion coefficients. It has been established that Non-Fickian diffusion mechanism has occurred for the release of thiram from these polymeric matrices. Furthermore, the initial rate of diffusion of thiram from these polymeric matrices is more as compared to the late stages of diffusion, which is analogous to the trends obtained for the diffusion of water molecules from these polymer matrices.     

New methodologies for security risk assessment of oil and gas industry

The oil and gas industry forms a vital and large part of the economy of any country. It provides crucial support to transport, manufacturing and energy sectors, produces valuable exports and provides huge employment. This industry along with fertilizer plants, petrochemical plants, etc., which handle hazardous chemicals, are potential targets for deliberate actions by terrorists, criminals and disgruntled employees. The process industries face different levels of threats. It is imperative to analyze the entire threat scenario before taking steps to counter it, otherwise each and every threat will have to be treated as most severe, thus resulting in a huge and wasteful expenditure.The Security Risk Factor Table (SRFT) and a Stepped Matrix Procedure (SMP) have been developed to assess the security risk of oil and gas industry as well as the other chemical process industries. While the SRFT deals with the effects of individual threats, the SMP deals with the cascading/domino effects which a lone, low probability event can cause. A case study of a refinery has been performed to show the application of the ideas presented.