Search results for: in-situ chemical oxidation

Authors: Xiaoqing Liu, Kurt Friese, Karsten Rinke

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Lacustrine sediment archives rich paleoenvironmental information in lake and surrounding environment. Additionally, modern sediment is used as an effective medium for the monitoring of lake. Organic carbon in sediment is a heterogeneous mixture with varying turnover times and qualities which result from the different biogeochemical processes in the deposition of organic material. Therefore, the isolation of different carbon pools is important for the research of lacustrine condition in the lake. However, the numeric available fractionation procedures can hardly yield homogeneous carbon pools on terms of stability and age. In this work, a multi-step fractionation protocol that treated sediment with hot water, HCl, H2O2 and Na2S2O8 in sequence was adopted, the treated sediment from each step were analyzed for the isotopic and structural compositions with Isotope Ratio Mass Spectrometer coupled with element analyzer (IRMS-EA) and Solid-state 13C Nuclear Magnetic Resonance (NMR), respectively. The sequential extractions with hot-water, HCl, and H2O2 yielded a more homogeneous and C3 plant-originating OC fraction, which was characterized with an atomic C/N ratio shift from 12.0 to 20.8, and 13C and 15N isotopic signatures were 0.9‰ and 1.9‰ more depleted than the original bulk sediment, respectively. Additionally, the H2O2- resistant residue was dominated with stable components, such as the lignins, waxes, cutans, tannins, steroids and aliphatic proteins and complex carbohydrates. 6M HCl in the acid hydrolysis step was much more effective than 1M HCl to isolate a sedimentary OC fraction with higher degree of homogeneity. Owing to the extremely high removal rate of organic matter, the step of a Na2S2O8 oxidation is only suggested if the isolation of the most refractory OC pool is mandatory. We conclude that this multi-step chemical fractionation procedure is effective to isolate more homogeneous OC pools in terms of stability and functional structure, and it can be used as a promising method for OC pools fractionation of sediment or soil in future lake research.

Keywords: 13C-CPMAS-NMR, 13C signature, lake sediment, OC fractionation

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Authors: Lucia Steenkamp, Chris V. D. Westhuyzen, Kgama Mathiba

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Ambergris, and more specifically its oxidation product (–)-ambrafuran, is a scarce, valuable, and sought-after perfumery ingredient. The material is used as a fixative agent to stabilise perfumes in formulations by reducing the evaporation rate of volatile substances. Ambergris is a metabolic product of the sperm whale (Physeter macrocephatus L.), resulting from intestinal irritation. Chemically, (–)-ambrafuran is produced from the natural product sclareol in eight synthetic steps – in the process using harsh and often toxic chemicals to do so. An overall yield of no more than 76% can be achieved in some routes, but generally, this is lower. A new 'green' route has been developed in our laboratory in which sclareol, extracted from the Clary sage plant, is converted to (–)-ambrafuran in two steps with an overall yield in excess of 80%. The first step uses a microorganism, Hyphozyma roseoniger, to bioconvert sclareol to an intermediate diol using substrate concentrations up to 50g/L. The yield varies between 90 and 67% depending on the substrate concentration used. The purity of the diol product is 95%, and the diol is used without further purification in the next step. The intermediate diol is then cyclodehydrated to the final product (–)-ambrafuran using a zeolite, which is not harmful to the environment and is readily recycled. The yield of the product is 96%, and following a single recrystallization, the purity of the product is > 99.5%. A preliminary LC-MS study of the bioconversion identified several intermediates produced in the fermentation broth under oxygen-restricted conditions. Initially, a short-lived ketone is produced in equilibrium with a more stable pyranol, a key intermediate in the process. The latter is oxidised under Norrish type I cleavage conditions to yield an acetate, which is hydrolysed either chemically or under lipase action to afford the primary fermentation product, an intermediate diol. All the intermediates identified point to the likely CYP450 action as the key enzyme(s) in the mechanism. This invention is an exceptional example of how the power of biocatalysis, combined with a mild, benign chemical step, can be deployed to replace a total chemical synthesis of a specific chiral antipode of a commercially relevant material.

Keywords: ambrafuran, biocatalysis, fragrance, microorganism

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Authors: Fatima Benchikh-Amiraa, Hocine Laouerb, Smain Amiraa, Guido Flaminic

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The essential oils of the aerial parts of Lavandula multifida and L. stoechas were extracted at the full bloom stage by hydrodistillation and theirs chemical compositions were estimated by means of gas chromatography–mass spectrometry (GC–MS). A total of 46 and 67 constituents were identified representing 95.5% and 98.2% of the total oils, respectively. The main components of L. multifida oil were carvacrol (63.8%), beta-bisabolene (8.7%), spathulenol (6.2%), caryophyllene oxide (3.6%) and linalool (2.9%). The oil of L. stoechas was dominated by fenchone (63.9%), camphor (7.8%), 1,8-cineole (5.3%) and myrtenyl acetate (4.2).

Keywords: essential oils, Lavandula multifida, Lavandula stoechas, chemical and molecular engineering

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Authors: Asif Jan

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Sodium hypochlorite (NaClO) is a common cleaning agent for ultrafiltration (UF) membranes. While its detrimental effects on polymeric membranes are well-documented, its impact on ceramic membranes remains less explored. This study investigates the chemical stability of silicon carbide (SiC) UF membranes prepared using low-pressure chemical vapor deposition (LP-CVD) during prolonged NaClO exposure. SiC UF membranes were fabricated via LP-CVD at two different temperature and pressure conditions. LP-CVD offers the advantage of SiC membrane fabrication at significantly lower temperatures (700-900°C) compared to conventional methods. The membranes were subjected to 200 hours of NaClO aging to assess their resilience. Before and after aging, we evaluated the properties and performance of the SiC UF membranes to identify optimal LP-CVD conditions. Our findings show that SiC UF membranes produced at 860°C via LP-CVD exhibit exceptional resistance to NaClO aging, whereas those prepared at 750°C experience significant deterioration. This highlights the crucial role of precise LP-CVD parameters in ensuring the robustness and long-term performance of SiC membranes in harsh chemical cleaning environments.

Keywords: ceramic membranes, ultrafiltration membranes, wastewater treatment, chemical vapor deposition

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Authors: Kanik Sharma

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In the year of 2011, the global production of carbon nano-materials (CNMs) was around 3,500 tons, and it is projected to expand at a compound annual growth rate of 30.6%. Expanding markets for applications of CNMs, such as carbon nano-tubes (CNTs) and carbon nano-fibers (CNFs), place ever-increasing demands on lowering their production costs. Current technologies for CNM generation require intensive premium feedstock consumption and employ costly catalysts; they also require input of external energy. Industrial-scale CNM production is conventionally achieved through chemical vapor deposition (CVD) methods which consume a variety of expensive premium chemical feedstocks such as ethylene, carbon monoxide (CO) and hydrogen (H2); or by flame synthesis techniques, which also consume premium feedstock fuels. Additionally, CVD methods are energy-intensive. Renewable and replenishable feedstocks, such as those found in municipal, industrial, agricultural recycling streams have a more judicious reason for usage, in the light of current emerging needs for sustainability. Agricultural sugarcane bagasse and corn residues, scrap tire chips as well as post-consumer polyethylene (PE) and polyethylene terephthalate (PET) bottle shreddings when either thermally treated by sole pyrolysis or by sequential pyrolysis and partial oxidation result in the formation of gaseous carbon-bearing effluents which when channeled into a heated reactor, produce CNMs, including carbon nano-tubes, catalytically synthesized therein on stainless steel meshes. The structure of the nano-material synthesized depends on the type of feedstock available for pyrolysis, and can be determined by analysing the feedstock. These feedstocks could supersede the use of costly and often toxic or highly-flammable chemicals such as hydrocarbon gases, carbon monoxide and hydrogen, which are commonly used as feedstocks in current nano-manufacturing process for CNMs.

Keywords: nanomaterials, waste plastics, sugarcane bagasse, pyrolysis

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Authors: Rehin Sulay, Anandhu Krishna, Jintumol Mathew, Vibin Ipe Thomas

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N-Nitrosodimethyl amine, the simplest member of the N-Nitrosoamine family, is a carcinogenic and mutagenic agent that has gained considerable research interest owing to its toxic nature. Ozonation of industrially important hydrazines such as unsymmetrical dimethylhydrazine (UDMH) or monomethylhydrazine (MMH) has been associated with NDMA formation and accumulation in the environment. UDMH/MMH - ozonation also leads to several other transformation products such as acetaldehyde dimethyl hydrazone (ADMH), tetramethyl tetra azene (TMT), diazomethane, methyl diazene, etc, which can be either precursors or competitors for NDMA formation.In this work, we explored the formation mechanism of ADMH and TMT from UDMH-ozonation and their further oxidation to NDMA using the second-order Moller Plesset perturbation theory employing the 6-311G(d) basis set. We have also investigated how MMH selectively forms methyl diazene and diazomethane under normal conditions and NDMA in the presence of excess ozone. Our calculations indicate that the reactions proceed via an initial H abstraction from the hydrazine –NH2 group followed by the oxidation of the generated N-radical species. The formation of ADMH from the UDMH-ozone reaction involves an acetaldehyde intermediate, which then reacts with a second UDMH molecule to generate ADMH. The preferable attack of ozone molecule on N=C bond of ADMH generates DMAN intermediate, which subsequently undergoes oxidation to form NDMA. Unlike other transformation products, TMT formation occurs via the dimerization of DMAN. Though there exist a N=N bonds in the TMT, which are preferable attacking sites for ozone, experimental studies show the lower yields of NDMA formation, which corroborates with the high activation barrier required for the process(42kcal/mol).Overall, our calculated results agree well with the experimental observations and rate constants. Computational calculations bring insights into the electronic nature and kinetics of the elementary reactions of this pathway, enabled by computed energies of structures that are not possible to access experimentally.

Keywords: reaction mechanism, ozonation, substituted hydrazine, transition state

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Authors: Elackiya Sithamparanathan

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Chemical agents used during the Sri Lankan civil war continue to threaten human and environmental health as affected areas are re-settled. Bioremediation is a cost-effective and eco-friendly approach to degrading chemical agents, and has greater public acceptance than chemical degradation. Baseline data on contaminant distribution, environmental parameters, and indigenous microbes are required before bioremediation can commence. The culture and isolate of suitable microbes and enzymes should be followed by laboratory trials, before field application and long-term monitoring of contaminant concentration, soil parameters, microbial ecology, and public health to monitor environmental and public health. As local people are not aware of the persistence of warfare chemicals and do not understand the potential impacts on human health, community awareness programs are required. Active community participation, and collaboration with international and local agencies, would contribute to the success of bioremediation and the effective removal of chemical agents in war affected areas of Sri Lanka.

Keywords: bioremediation, environmental protection, human health, war affected regions in Sri Lanka

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Authors: E. E. Tereshatov, M. Yu. Boltoeva, V. Mazan, M. F. Volia, C. M. Folden III

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Room temperature ionic liquids (RTILs) are a class of liquid organic salts with melting points below 20 °C that are considered to be environmentally friendly ‘designers’ solvents. Pure hydrophobic ILs are known to extract metallic species from aqueous solutions. The closest analogues of ionic liquids are deep eutectic solvents (DESs), which are a eutectic mixture of at least two compounds with a melting point lower than that of each individual component. DESs are acknowledged to be attractive for organic synthesis and metal processing. Thus, these non-volatile and less toxic compounds are of interest for critical metal extraction. The US Department of Energy and the European Commission consider indium as a key metal. Its chemical homologue, thallium, is also an important material for some applications and environmental safety. The aim of this work is to systematically investigate In and Tl extraction from aqueous solutions into pure fluorinated ILs and hydrophobic DESs. The dependence of the Tl extraction efficiency on the structure and composition of the ionic liquid ions, metal oxidation state, and initial metal and aqueous acid concentrations have been studied. The extraction efficiency of the TlXz3–z anionic species (where X = Cl– and/or Br–) is greater for ionic liquids with more hydrophobic cations. Unexpectedly high distribution ratios (> 103) of Tl(III) were determined even by applying a pure ionic liquid as receiving phase. An improved mathematical model based on ion exchange and ion pair formation mechanisms has been developed to describe the co-extraction of two different anionic species, and the relative contributions of each mechanism have been determined. The first evidence of indium extraction into new quaternary ammonium- and menthol-based hydrophobic DESs from hydrochloric and oxalic acid solutions with distribution ratios up to 103 will be provided. Data obtained allow us to interpret the mechanism of thallium and indium extraction into ILs and DESs media. The understanding of Tl and In chemical behavior in these new media is imperative for the further improvement of separation and purification of these elements.

Keywords: deep eutectic solvents, indium, ionic liquids, thallium

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Authors: Guillaume Caulier, Lola Brasseur, Patrick Flammang, Pascal Gerbaux, Igor Eeckhaut

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Saponins and quinones are two major groups of secondary metabolites widely distributed in the biosphere. More specifically, triterpenoid saponins and anthraquinones are mainly found in a wide variety of plants, bacteria and fungi. In the animal kingdom, these natural organic compounds are rare and only found in small quantities in arthropods, marine sponges and echinoderms. In this last group, triterpenoid saponins are specific to holothuroids (sea cucumbers) while anthraquinones are the chemical signature of crinoids (feather stars). Depending on the species, they present different molecular cocktails. Despite presenting different chemical properties, these molecules share numerous similarities. This study compares the biological distribution, the pharmacological effects and the ecological roles of holothuroid saponins and crinoid anthraquinones. Both of them have been defined as allomones repelling predators and parasites (i.e. chemical defense) and have interesting pharmacological properties (e.g. anti-bacterial, anti-fungal, anti-cancer). Our study investigates the chemical ecology of two symbiotic associations models; between the snapping shrimp Synalpheus stimpsonii associated with crinoids and the Harlequin crab Lissocarcinus orbicularis associated with holothuroids. Using behavioral experiments in olfactometers, chemical extractions and mass spectrometry analyses, we discovered that saponins and anthraquinones present a second ecological role: the attraction of obligatory symbionts towards their hosts. They can, therefore, be defined as kairomones. This highlights a new paradigm in marine chemical ecology: Chemical repellents are attractants to obligatory symbionts because they constitute host specific chemical signatures.

Keywords: anthraquinones, kairomones, marine symbiosis, saponins, attractant

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Authors: Hak-Ryul Kim, Hyung-Geun Lee, Qi Long, Ching Hou

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Structural modification of natural lipids via chemical reaction or microbial bioconversion can change their properties or even create novel functionalities. Enzymatic oxidation of lipids leading to formation of oxylipin is one of those modifications. Hydroxy fatty acids, one of those oxylipins have gained important attentions because of their structural and functional properties compared with other non-hydroxy fatty acids. Recently 7,10-dihydroxy-8(E)-octadecenoic acid (DOD) was produced with high yield from lipid-containing oleic acid by microbial conversion, and the further study confirmed that DOD contained strong antimicrobial activities against a broad range of microorganisms. In this study, we tried to modify DOD molecules by the enzymatic or physical reaction to create new functionality or to enhance the antimicrobial activity of DOD. After modification of DOD molecules by different ways, we confirmed that the antimicrobial activity of DOD was highly enhanced and presented strong antimicrobial activities against multidrug-resistant Staphylococcus aureus, suggesting that DOD and its derivatives can be used as efficient antimicrobial agents for medical and industrial applications.

Keywords: biocatalysis, antimicrobial agent, multidrug-resistant bacteria, vegetable oil

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Authors: Ahmed O. Apampa, Yinusa A. Jimoh

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The paper examines the mechanism of pozzolan-soil reactions, using a recent study on the chemical stabilization of a Class A-2-7 (3) lateritic soil, with corn cob ash (CCA) as case study. The objectives are to establish a nexus between cation exchange capacity of the soil, the alkaline forming compounds in CCA and percentage CCA addition to soil beyond which no more improvement in strength properties can be achieved; and to propose feasible chemical reactions to explain the chemical stabilization of the lateritic soil with CCA alone. The lateritic soil, as well as CCA of pozzolanic quality Class C were separately analysed for their metallic oxide composition using the X-Ray Fluorescence technique. The cation exchange capacity (CEC) of the soil and the CCA were computed theoretically using the percentage composition of the base cations Ca²⁺, Mg²⁺ K⁺ and Na²⁺ as 1.48 meq/100 g and 61.67 meq/100 g respectively, thus indicating a ratio of 0.024 or 2.4%. This figure, taken as the theoretical amount required to just fill up the exchangeable sites of the clay molecules, compares well with the laboratory observation of 1.5% for the optimum level of CCA addition to lateritic soil. The paper went on to present chemical reaction equations between the alkaline earth metals in the CCA and the silica in the lateritic soil to form silicates, thereby proposing an extension of the theory of mechanism of soil stabilization to cover chemical stabilization with pozzolanic ash only. The paper concluded by recommending further research on the molecular structure of soils stabilized with pozzolanic waste ash alone, with a view to confirming the chemical equations advanced in the study.

Keywords: cation exchange capacity, corn cob ash, lateritic soil, soil stabilization

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Authors: Azizul Haque, Kamrun Nahar

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Field experiments were conducted to reduce the chemical fertilizers with the integrated use of straight and phospho- vermicompost with chemical fertilizers in T. aman-Boro rice cropping pattern at the BINA farm, Mymensingh during 2019-20. Six treatments were used in the experiment for both the crops. The treatments used for T. aman rice (Binadhan 17) with straight vermicompost were as follows: T1: Native soil fertility, T2: 100% N from Chemical Fertilizer (CF), T3:70%N from CF, T4: 30% N from vermicompost-3 + 70% N from CF and T5:30% N from vermicompost-4 + 70% N from CF and T6: 100% PKS only. The treatments of Boro rice (var. Binadhan -10) with phospho-vermicompost were: T1: Native soil fertility, T2: 100% NPKS from chemical fertilizer (CF), T3:75% NKS from CF (Non IPNS) with 1 t ha-1 Phospho-vermicompost (P-Vermicom), T4: 100% NKS (IPNS) with 2 t ha-1 P-Vermicom, T5: 100% NKS from CF (Non IPNS) with 2 t ha-1 P-Vermicom and T6: 100% NKS. The experiments were conducted in a Randomized Complete Block Design with three replications. The treatment T5 (5.5 t ha-1) gave maximum grain yield of T.aman rice followed by the treatment T4 (5.4 t ha-1). But the treatmentsT5, T4, and T2 gave identical grain yields of T. aman rice. Similar results were observed in case of straw yields of T. Aman rice. The result indicated that 70% N from CF with 30% N from either straight vermicompost-3 or straight vermicompost-4 gave comparable yield to the sole application of 100% N from CF alone. Therefore, 30% chemical fertilizers (N, P, K and S) could be saved with the integrated (IPNS) use of vermicompost-3 or vermicompost-4 in the cultivation of T. aman rice. Application of Phospho-vermicompost significantly influenced the yield and yield contributing characters of Boro rice (Binadhan-10). The treatment T4 (7.23.0 t ha-1) gave maximum grain yield of Boro rice followed by the treatments T2 and T5. But the treatments T2 and T5 produced statistically similar grain yields. The results from the treatment T4 (100% NKS (IPNS) with 2.0 t ha-1P-Vermicom) indicated that full demand of P could be met up from 2 t ha-1 Phospho-vermicompost with IPNS chemical fertilizers (NKS) which was sufficient for attaining the highest grain yield of Boro rice than that of the treatment T2 (100% NPKS from CF) and the treatmentT5 (100% NKS from CF (Non IPNS) + 2 t ha-1 Phospho-vermicompost). The results revealed that 100% P and substantial amount of N (21%), K (44.6%) and S (53.7%) fertilizers could be saved with the integrated use of Phospho-vermicompost in the cultivation of Boro rice. In case of Boro rice partial cost benefit analysis showed that the application of Phospho-vermicompost (@2 tha--1) with IPNS chemical fertilizes (NKS) gave higher return of Tk. 18,213 / - than that of only 100% chemical fertilizer. Therefore, use of Phospho-vermicompost was beneficial for the cultivation of Boro rice in combination with suitable dose of chemical fertilizers.

Keywords: phosphovermicompost, cropping pattern, rice yield, chemical fertilizer

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Authors: Vasant Reddy, Shivani A. Singh, Pravin S. More

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In the present investigation, we demonstrated the fabrication of few-layers of graphene sheets with alkali metal i.e. Rb-G using chemical route method. The obtained materials were characterized by means of chemical, structural and electrical techniques, using the ultraviolet-visible spectroscopy (UV-Vis), Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and 4 points probe, respectively. The XRD studies were carried out to understand the phase of the samples where we found a sharp peak of Rb-G at 26.470. UV-Spectroscopy of Graphene and Rb-modified graphene samples shows the absorption peaks at ~248 nm and ~318 nm respectively. These analyses show that this modified material can be useful for gas sensing applications and to be used in diverse areas.

Keywords: chemical route, graphene, gas sensing, UV-spectroscopy

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Authors: Mohannad N. H. Al-Malichi

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Because of its exceptional properties, graphene has become the most promising nanomaterial for the development of a new generation of advanced materials from battery electrodes to structural composites. However, current methods to meet requirements for the mass production of high-quality graphene are limited by harsh oxidation, high temperatures, and tedious processing steps. To extend the scope of the bulk production of graphene, herein, a facile, reproducible and cost-effective approach has been developed. This involved heating a specific mixture of chemical materials at an extremely low temperature (70 C) for a short period (7 minutes) to exfoliate functionalized graphene platelets with high structural integrity. The obtained graphene platelets have an average thickness of 3.86±0.71 nm and a lateral size less than ~2 µm with a low defect intensity ID/IG ~0.06. The thin film (~2 µm thick) exhibited a low surface resistance of ~0.63 Ω/sq⁻¹, confirming its high electrical conductivity. Additionally, these nanoplatelets were decorated with polar functional groups (epoxy and carboxyl groups), thus have the potential to toughen and provide multifunctional polymer nanocomposites. Moreover, such a simple method can be further exploited for the novel exfoliation of other layered two-dimensional materials such as MXenes.

Keywords: functionalized graphene nanoplatelets, high structural integrity graphene, low temperature exfoliation of graphene, functional graphene platelets

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Authors: Yesim Ozogul, Mustafa Durmuş, Fatih Ozogul, Esmeray Kuley Boğa, Yılmaz Uçar, Hatice Yazgan

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The effects of oil-in-water nanoemulsions on the sensory, chemical (total volatile basic nitrogen (TVB-N), thiobarbituric acid (TBA), peroxide value (PV) and free fatty acids (FFA), and microbiological qualities (total viable count (TVC), total psychrophilic bacteria, and total Enterbactericaea bacteria) of sea bream fillets stored at 2 ± 2°C were investigated. Physical properties of emulsions (viscosity, the particle size of droplet, thermodynamic stability, refractive index and surface tension) were determined. The results showed that the use of nanoemulsion extended the shelf life of fish 2 days when compared with the control. Treatment with nanoemulsions significantly (p<0.05) decreased the values of biochemical parameters during storage period. Bacterial growth was inhibited by the use of nanoemulsions. Based on the results, it can be concluded that nanoemulsions based on commercial oils extended the shelf life and improved the quality of sea bass fillets during storage period.

Keywords: lipid oxidation, nanoemulsion, sea bass, quality parameters

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Authors: Francis Machumi, Ester Innocent, Pius Yanda, Philip C. Stevenson

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Curative dependence of traditionally used medicinal plants on season of harvest is an alleged claim by traditional health practitioners. This study intended to verify these claims by investigating antifungal activity and chemical composition of traditionally used medicinal plants Turraea holstii and Clausena anisata harvested in rainy season and dry season. The antifungal activities were determined by broth microdilution method whereas chemical profiling of the extracts from the plant materials was done by gas chromatography (GC). Results indicated that extracts of plant materials harvested in dry season showed enhanced antifungal activity as compared to extracts of plant materials harvested in rainy season. GC chromatograms showed overalls increase in number and amount of chemical species for extracts of plant materials harvested in dry season as compared to extracts of plant materials harvested in rainy season.

Keywords: antifungal activity, chemical composition, medicinal plants, seasonal dependence

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Authors: Zahra Neffah, Henda Kahalerras

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A numerical study is made in a parallel-plate porous channel subjected to an oscillating flow and an exothermic chemical reaction on its walls. The flow field in the porous region is modeled by the Darcy–Brinkman–Forchheimer model and the finite volume method is used to solve the governing equations. The effects of the modified Frank-Kamenetskii (FKm) and Damköhler (Dm) numbers, the amplitude of oscillation (A), and the Strouhal number (St) are examined. The main results show an increase of heat and mass transfer rates with A and St, and their decrease with FKm and Dm.

Keywords: chemical reaction, heat and mass transfer, oscillating flow, porous channel

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Authors: Ntokozo Dambuza, Maryna Van De Venter, Trevor Koekemoer

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Oxidative stress contributes to the pathogenesis of many diseases and consequently antioxidant therapy has attracted much attention as a potential therapeutic strategy. Regardless of the quantities ingested, antioxidants need to reach the diseased tissues at concentrations sufficient to combat oxidative stress. Bioavailability is thus a defining criterion for the therapeutic efficacy of antioxidants. In addition, therapeutic antioxidants must possess biologically relevant characteristics which can target the specific molecular mechanisms responsible for disease related oxidative stress. While many chemical antioxidant assays are available to quantify antioxidant capacity, they relate poorly to the biological environment and provide no information as to the bioavailability. The present comparative study thus aims to characterise green and fermented rooibos extracts, well recognized for their exceptional antioxidant capacity, in terms of antioxidant bioavailability and efficacy in a disease relevant cellular setting. Chinese green tea antioxidant activity was also evaluated. Chemical antioxidant assays (FRAP, DPPH and ORAC) confirmed the potent antioxidant capacity of both green and fermented rooibos, with green rooibos possessing antioxidant activity superior to that of fermented rooibos and Chinese green tea. Bioavailability was assessed using the PAMPA assay and the results indicate that green and fermented rooibos have a permeation coefficient of 5.7 x 10-6 and 6.9 x 10-6 cm/s, respectively. Chinese green tea permeability coefficient was 8.5 x 10-6 cm/s. These values were comparable to those of rifampicin, which is known to have a high permeability across intestinal epithelium with a permeability coefficient of 5 x 10 -6 cm/s. To assess the antioxidant efficacy in a cellular context, U937 and red blood cells were pre-treated with rooibos and Chinese green tea extracts in the presence of a dye DCFH-DA and then exposed to oxidative stress. Green rooibos exhibited highest activity with an IC50 value of 29 μg/ml and 70 μg/ml, when U937 and red blood cells were exposed oxidative stress, respectively. Fermented rooibos and Chinese green tea had IC50 values of 61 μg/ml and 57 μg/ml for U937, respectively, and 221 μg/ml and 405 μg/ml for red blood cells, respectively. These results indicate that fermented and green rooibos extracts were able to permeate the U937 cells and red blood cell membrane and inhibited oxidation of DCFH-DA to a fluorescent DCF within the cells.

Keywords: rooibos, antioxidants, permeability, bioavailability

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Authors: Chiung-Chin Huang, Jui-Yen Lin, Yao-Hui Huang

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Among current techniques of boron removal from wastewater with high boron concentration, chemical oxo-precipitation (COP) is one of the promising methods due to its milder condition. COP uses H2O2 to transform boric acid to perborates which can easily precipitate with barium ions at room temperature. However, the generation of the waste sludge that requires sludge/water separation and sludge dewatering is troublesome. This work presents an innovative technology which integrates chemical oxo-precipitation (COP) with fluidized-bed homogeneous granulation (FBHG) to reclaim boron as homogeneous perborate particles. By conducting COP in a fluidized-bed reactor, the barium perborate can be granulated to form homogeneous particles (>1.0 mm) with low water content (< 10%). Under the suitable condition, more than 70% of boron can be recovered from 600 ppm of boron solution and the residual boron is lower than 100 ppm.

Keywords: barium, perborate, chemical oxo-precipitation, boron removal, fluidized-bed, granulation

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Authors: Escada A. L. A., Pereira C. A., Jorge A. O. C., Alves Claro A. P. R.

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In the present work, a susceptibility and efficacy of the Ti–7.5Mo alloy nanotube and Ti–7.5Mo alloy to bacterial biofilm formation after surface treatment was evaluated. The Ti–7.5Mo alloy was obtained in arc furnace under an argon atmosphere. Ingots were then homogenized under vacuum at 1100 ◦C for 86.4 ks to eliminate chemical segregation and after cold worked discs were cutting. Nanotubes were processed using anodic oxidation in 0.25% NH4F electrolyte solution. Biofilms were grown in discs immersed in sterile brain heart infusion broth (BHI) containing 5% sucrose, inoculated with microbial suspension (106 cells/ml) and incubated for 5 days. Next, the discs were placed in tubes with sterile physiological solution 0.9% sodium chloride (NaCl) and sonicated for to disperse the biofilms. Tenfold serial dilutions were carried and aliquots seeded in selective agar, which were then incubated for 48 h. Then, the numbers CFU/ml (log 10) were counted and analyzed statistically. Scanning electron microscopy (SEM) on discs with biofilms groupswas performed, atomic force microscope (AFM) and contact angle. The results show that there is no difference in bacterial adhesion between Ti–7.5Mo alloy nanotube pure titanium and Ti–7.5Mo alloy.

Keywords: biofilm, titanium alloy, brain heart infusion, scanning electron microscopy

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Authors: Yao-Hui Huang, Ming-Chun Yen, Jui-Yen Lin, Yu-Jen Shih

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This work investigated the reclamation of boron in industrial wastewaters by a chemical oxo-precipitation (COP) technique at room temperature. In COP, the boric acid was pretreated with H₂O₂, yielding various perborate anions. Afterwards, calcium chloride was used to efficiently remove boron through precipitation of calcium perborate. The important factors included reacted pH and the molar ratio of [Ca]/[B]. Under conditions of pH 11 and [Ca]/[B] of 1, the boron concentration could be reduced immediately from 600 ppm to 50 ppm in 10 minutes. The boron removal was enhanced with a higher [Ca]/[B], which further reduced boron to 20 ppm in 10 minutes. Nevertheless, the dissolution of carbon dioxide potentially affected the efficacy of COP and increased the boron concentration after 10 minutes.

Keywords: chemical oxo-precipitation, boron, carbon dioxide, hydrogen peroxide

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Authors: Łukasz Mazur, Kamil Domaradzki, Maciej Bik, Tomasz Brylewski, Aleksander Gil

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Interconnects used in solid oxide fuel and electrolyzer cells (SOFCₛ/SOECs) serve several important functions, and therefore interconnect materials must exhibit certain properties. Their thermal expansion coefficient needs to match that of the ceramic components of these devices – the electrolyte, anode and cathode. Interconnects also provide structural rigidity to the entire device, which is why interconnect materials must exhibit sufficient mechanical strength at high temperatures. Gas-tightness is also a prerequisite since they separate gas reagents, and they also must provide very good electrical contact between neighboring cells over the entire operating time. High-chromium ferritic steels meets these requirements to a high degree but are affected by the formation of a Cr₂O₃ scale, which leads to increased electrical resistance. The final criterion for interconnect materials is chemical inertness in relation to the remaining cell components. In the case of ferritic steels, this has proved difficult due to the formation of volatile and reactive oxyhydroxides observed when Cr₂O3 is exposed to oxygen and water vapor. This process is particularly harmful on the cathode side in SOFCs and the anode side in SOECs. To mitigate this, protective-conducting ceramic coatings can be deposited on an interconnect's surface. The area-specific resistance (ASR) of a single interconnect cannot exceed 0.1 m-2 at any point of the device's operation. The rate at which the CrO₃ scale grows on ferritic steels can be reduced significantly via the so-called reactive element effect (REE). Research has shown that the deposition of Gd₂O₃ nanoparticles on the surface of the Crofer 22 APU, already modified using a protective-conducting spinel layer, further improves the oxidation resistance of this steel. However, the deposition of the manganese-cobalt spinel layer is a rather complex process and is performed at high temperatures in reducing and oxidizing atmospheres. There was thus reason to believe that this process may reduce the effectiveness of Gd₂O₃ nanoparticles added as an active element source. The objective of the present study was, therefore, to determine any potential impact by introducing a preoxidation stage after the nanoparticle deposition and before the steel is coated with the spinel. This should have allowed the nanoparticles to incorporate into the interior of the scale formed on the steel. Different samples were oxidized for 7000 h in air at 1073 K under quasi-isothermal conditions. The phase composition, chemical composition, and microstructure of the oxidation products formed on the samples were determined using X-ray diffraction, Raman spectroscopy, and scanning electron microscopy combined with energy-dispersive X-ray spectroscopy. A four-point, two-probe DC method was applied to measure ASR. It was found that coating deposition does indeed reduce the beneficial effect of Gd₂O₃ addition, since the smallest mass gain and the lowest ASR value were determined for the sample for which the additional preoxidation stage had been performed. It can be assumed that during this stage, gadolinium incorporates into and segregates at grain boundaries in the thin Cr₂O₃ that is forming. This allows the Gd₂O₃ nanoparticles to be a more effective source of the active element.

Keywords: interconnects, oxide nanoparticles, reactive element effect, SOEC, SOFC

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Authors: Ádám Vass, István Bakos, Irina Borbáth, Zoltán Pászti, István Sajó, András Tompos

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Important requirements for the anode side electrocatalysts of polymer electrolyte membrane (PEM) fuel cells are CO-tolerance, stability and corrosion resistance. Carbon is still the most common material for electrocatalyst supports due to its low cost, high electrical conductivity and high surface area, which can ensure good dispersion of the Pt. However, carbon becomes degraded at higher potentials and it causes problem during application. Therefore it is important to explore alternative materials with improved stability. Molybdenum-oxide can improve the CO-tolerance of the Pt/C catalysts, but it is prone to leach in acidic electrolyte. The Mo was stabilized by isovalent substitution of molybdenum into the rutile phase titanium-dioxide lattice, achieved by a modified multistep sol-gel synthesis method optimized for preparation of Ti0.7Mo.3O2-C composite. High degree of Mo incorporation into the rutile lattice was developed. The conductivity and corrosion resistance across the anticipated potential/pH window was ensured by mixed oxide – activated carbon composite. Platinum loading was carried out using NaBH4 and ethylene glycol; platinum content was 40 wt%. The electrocatalyst was characterized by both material investigating methods (i.e. XRD, TEM, EDS, XPS techniques) and electrochemical methods (cyclic-voltammetry, COads stripping voltammetry, hydrogen oxidation reaction on rotating disc electrode). The electrochemical activity of the sample was compared to commercial 40 wt% Pt/C (Quintech) and PtRu/C (Quintech, Pt= 20 wt%, Ru= 10 wt%) references. Enhanced CO tolerance of the electrocatalyst prepared using the Ti0.7Mo.3O2-C composite material was evidenced by the appearance of a CO-oxidation related 'pre-peak' and by the pronounced shift of the maximum of the main CO oxidation peak towards less positive potential compared to Pt/C. Fuel cell polarization measurements were also carried out using Bio-Logic and Paxitech FCT-150S test device. All details on the design, preparation, characterization and testing by both electrochemical measurements and fuel cell test device of electrocatalyst supported on Ti0.7Mo.3O2-C composite material will be presented and discussed.

Keywords: anode electrocatalyst, composite material, CO-tolerance, TiMoOx

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Authors: Mohammedi Ferhate, Hakim Chadli, Laggoun Chaouki

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The main objectives of work in this area are, first, obtaining the high laser energies in short time durations needed for the feasibility studies of laser induced thermodynamically exothermic chemical reactions , second, investigating the physical principles that can be used to make laser sources capable of delivering high average powers. We note that, in order to reach both objectives, one has to convert electrical or chemical energy into laser energy, using dense gaseous media.. We present results from the early development of an F atom source appropriate for HF and DF chemical laser research. We next explain the very important difficulties encountered in working with dense gases for that purpose, and we shall describe how, especially at Evaluation of downstream-mixing scheme –levels transitions (001) → (100) and (001) → (020) gas dynamic laser The physical phenomena that control the operation of presently existing laser devices are now sufficiently well understood, so that it is possible to predict that new generations of lasers could be designed in the future. The proposed model of excitation and relaxation levels was finally proved by the computational numerical code of Matlab toolboxes of different parameters of nozzle.

Keywords: hydrogen, combust, chemical laser, halogen atom

Procedia PDF Downloads 51

Authors: Sajad A. Rather, F. A. Masoodi, Rehana Akhter, S. M. Wani, Adil Gani

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Modern trend towards convenience foods has resulted in increased production and consumption of restructured meat products and are of great importance to the meat industry. In meat products fat plays an important role in cooking properties, texture & sensory scores, however, high fat contents in particular animal fats provide high amounts of saturated fatty acids and cholesterol and are associated with several types of non communicable diseases such as obesity, hypertension and coronary heart diseases. Thus, fat reduction has generally been seen as an important strategy to produce healthier meat products. This study examined the effects of reducing fat level from 20% to 10% and substituting mutton back fat with guar gum (0.5%, 1% & 1.5%) on cooking properties, proximate composition, lipid and protein oxidation, texture, microstructure and sensory characteristics of goshtaba- a traditional meat product of J & K, India were investigated and compared with high fat counterparts. Reduced- fat goshtaba samples containing guar gum had significantly (p ≤ 0.05) higher yield, less shrinkage, more moisture retention and more protein content than the control sample. TBARs and protein oxidation (carbonyl content) values of the control was significantly (p ≤ 0.05) higher than reduced fat goshtaba samples and showed a positive correlation between lipid and protein oxidation. Hardness, gumminess & chewiness of the control (20%) were significantly higher than reduced fat goshtaba samples. Microstructural differences were significant (p ≤ 0.05) between control and treated samples due to an increased moisture content in the reduced fat samples. Sensory evaluation showed significant (p ≤ 0.05) reduction in texture, flavour and overall acceptability scores of treatment products; however the scores for 0.5% and 1% treated samples were in the range of acceptability. Guar gum may also be used as a source of soluble dietary fibre in food products and a number of clinical studies have shown a reduction in postprandial glycemia and insulinemia on consumption of guar gum, with the mechanism being attributed to an increased transit time in the stomach and small intestine, which may have been due to the viscosity of the meal hindering the access of glucose to the epithelium.

Keywords: goshtaba, guar gum, traditional, fat reduction, acceptability

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Authors: O. Balamane-Zizi, L. M. Rouidi, A. Boukhrissa, N. Daas, H. Ait-amar

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The objective of this study was to test the possibility of a mixed treatment (physical-chemical and biological) of Ouled Fayet leachates which date of 10 years and has a large fraction of hard COD that can be reduced by coagulation-flocculation. Previous batch tests showed the possibility of applying the physical-chemical and biological treatments separately; the removal efficiencies obtained in this case were not interesting. We propose, therefore, to test the possibility of a combined treatment, in order to improve the quality of the leachates. Estimation of the treatment’s effectiveness was done by analysis of some pollution parameters such as COD, suspended solids, and heavy metals (particularly iron and nickel). The main results obtained after the combination of treatments, show reduction rate of about 63% for COD, 73% for suspended solids and 80% for iron and nickel. We also noted an improvement in the turbidity of treated leachates.

Keywords: landfill leachates, COD, physical-chemical treatment, biological treatment

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Authors: Ghulam Mustafa Peerzada, Shagufta Rashid, Nadeem Bashir

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These the influence of initial reagent concentrations on the Belousov-Zhabotinsky (BZ) system with Mn2+/Mn3+ as redox catalyst, inorganic bromate as oxidant and pyrogallol as organic substrate was studied. The reactions were monitored by potentiometery in oxidation reduction potential (ORP) mode. The aforesaid reagents were mixed with varying concentrations to evolve the optimal concentrations at which the reaction system exhibited better oscillations. The various oscillatory parameters such as induction period (tin), time period (tp), frequency (v), amplitude (A) and number of oscillations (n) were derived and the dependence of concentration of the reacting species on these oscillatory parameters was interpreted on the basis of the Field-Koros-Noyes mechanism. Ferroin based BZ system with pyrogallol as organic substrate was optimized under CSTR condition at temperature of 30±0.1oC Effect of molecules like monomer and polymer as additives to the system was checked and their interaction with the system was also studied. It has been observed that the monomer affects the time period, while the polymer has its effect on the amplitude of oscillations because of monomer’s interaction with the bromine and polymer’s with that of the Ferroin.

Keywords: Belousov Zhabotinsky reaction, oscillatory parameters, polymer, pyrogallol

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Authors: C. C. Igwe

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Several parts of Neem tree (Azadirachta indica) are used in traditional medicine in many West African countries for the treatment of various human diseases. The leaf, stem - bark and seed were air dried for 8, 5 and 7 days, respectively. The shells were carfully separated from the seeds, each powdered sample obtained with mechanical miller and 250 mm sieve. The neem samples were individually subjected to extraction with acetone, n-hexane for 48hr and 72 hr, respectively. Physico-chemical and antibacterial evaluation were carried out using standard methods. Results of physico - chemical analyses of the extracted oil from the seed shows that it has a brownish colour, with a smell similar to garlic while the moisture content, refractive index are 0.76% and 1.47 respectively. Other vital chemical results obtained from the neem oil such as saponification value (234.62), acid value (10.84 %), free fatty acid (5.84 %) and peroxide value (10.52%) indicated the oil extracted satisfied standard oils parameters for quality soap and cosmetics production. The antibacterial screening by disc diffusion revealed the oil demonstrated high activity against Staphylococcus aureus. Both the physio-chemical and antibacterial of samples have been certified by National Agency for Food and Drugs Administration and Control. The preliminary results of this study may validate the medicinal value of the plant. Further studies are in progress to clarify the in vivo potentials of neem extracts in the management of human communicable diseases and this is a subject of investigation in our group.

Keywords: anti-bacterial, neem extract, physico-chemical analyses, staphylococcus aureus

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Authors: Jatindra Lahkar

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The effect of chemical reaction on laminar mixed convection flow and heat and mass transfer along a vertical unsteady stretching sheet is investigated, in the presence of heat generation/absorption with variable viscosity and viscous dissipation. The governing non-linear partial differential equations are reduced to ordinary differential equations using similarity transformation and solved numerically using the fourth order Runge-Kutta method along with shooting technique. The effects of various flow parameters on the velocity, temperature and concentration distributions are analyzed and presented graphically. Skin-friction coefficient, Nusselt number and Sherwood number are derived at the sheet. It is observed that the influence of chemical reaction, the fluid flow along the sheet accelerate with the increase of chemical reaction parameter, on the other hand, temperature of the fluid increases with increase of chemical reaction parameter but concentration of the fluid reduces with it. The boundary layer decreases on the surface of the sheet for all values of unsteadiness parameter, increasing values of the chemical reaction parameter. The increases in the values of Sc cause the species concentration and its boundary layer thickness to decrease resulting in less induced flow and higher fluid temperatures. This is depicted in the decreases in the velocity and species concentration and increases in the fluid temperature as Sc increases.

Keywords: chemical reaction, heat generation/absorption, magnetic number, unsteadiness, variable viscosity

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Authors: Bilal Murtaza, Xiaoyu Li, Liming Dong, Muhammad Kashif Saleemi, Gen Li, Bowen Jin, Lili Wang, Yongping Xu

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Fusarium spp. produce numerous mycotoxins, such as zearalenone (ZEN), deoxynivalenol (DON), and its acetylated compounds, 3-acetyl-deoxynivalenol (3-ADON) and 15-acetyl-deoxynivalenol (15-ADON) (15-ADON). In a co-culture system, the soil-derived Escherichia marmotae strain degrades ZEN and DON into 3-keto-DON and DOM-1 via enzymatic deep-oxidation. When pure mycotoxins were subjected to Escherichia marmotae in culture flasks, degradation, and detoxification were also attained. DON and ZEN concentrations, ambient pH, incubation temperatures, bacterium concentrations, and the impact of acid treatment on degradation were all evaluated. The results of the ELISA and high-performance liquid chromatography-electrospray ionization-high resolution mass spectrometry (HPLC-ESI-HRMS) tests demonstrated that the concentration of mycotoxins exposed to Escherichia marmotae was significantly lower than the control. ZEN levels were reduced by 43.9%, while zearalenone sulfate ([M/z 397.1052 C18H21O8S1) was discovered as a derivative of ZEN converted by microbes to a less toxic molecule. Furthermore, Escherichia marmotae appeared to metabolize DON 35.10% into less toxic derivatives (DOM-1 at m/z 281 of [DON - O]+ and 3-keto-DON at m/z 295 of [DON - 2H]+). These results show that Escherichia marmotae can reduce Fusarium mycotoxins production, degrade pure mycotoxins, and convert them to less harmful compounds, opening up new possibilities for study and innovation in mycotoxin detoxification.

Keywords: mycotoxins, zearalenone, deoxynivalenol, bacterial degradation

Procedia PDF Downloads 66