Search results for: toxic cyanobacteria

Authors: Aneta Maćczak, Bożena Bukowska, Jaromir Michałowicz

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Bisphenols are one of the most widely used chemical compounds worldwide. They are used in the manufacturing of polycarbonates, epoxy resins and thermal paper which are applied in plastic containers, bottles, cans, newspapers, receipt and other products. Among these compounds, bisphenol A (BPA) is produced in the highest amounts. There are concerns about endocrine impact of BPA and its other toxic effects including hepatotoxicity, neurotoxicity and carcinogenicity on human organism. Moreover, BPA is supposed to increase the incidence the obesity, diabetes and heart disease. For this reason the use of BPA in the production of plastic infant feeding bottles and some other consumers products has been restricted in the European Union and the United States. Nowadays, BPA analogues like bisphenol F (BPF) and bisphenol S (BPS) have been developed as alternative compounds. The replacement of BPA with other bisphenols contributed to the increase of the exposure of human population to these substances. Toxicological studies have mainly focused on BPA. In opposite, a small number of studies concerning toxic effects of BPA analogues have been realized, which makes impossible to state whether those substituents are safe for human health. Up to now, the mechanism of bisphenols action on the erythrocytes has not been elucidated. That is why, the aim of this study was to assess the effect of BPA and its selected analogues such as BPF and BPS on the activity of antioxidant enzymes, i.e. catalase (EC 1.11.1.6.), glutathione peroxidase (E.C.1.11.1.9) and superoxide dismutase (EC.1.15.1.1) in human erythrocytes. Red blood cells in respect to their function (transport of oxygen) and very well developed enzymatic and non-enzymatic antioxidative system, are useful cellular model to assess changes in redox balance. Erythrocytes were incubated with BPA, BPF and BPS in the concentration ranging from 0.5 to 100 µg/ml for 24 h. The activity of catalase was determined by the method of Aebi (1984). The activity of glutathione peroxidase was measured according to the method described by Rice-Evans et al. (1991), while the activity of superoxide dismutase (EC.1.15.1.1) was determined by the method of Misra and Fridovich (1972). The results showed that BPA and BPF caused changes in the antioxidative enzymes activities. BPA decreased the activity of examined enzymes in the concentration of 100 µg/ml. We also noted that BPF decreased the activity of catalase (5-100 µg/ml), glutathione peroxidase (50-100 µg/ml) and superoxide dismutase (25-100 µg/ml), while BPS did not cause statistically significant changes in investigated parameters. The obtained results suggest that BPA and BPF disrupt redox balance in human erythrocytes but the observed changes may occur in human organism only during occupational or subacute exposure to these substances.

Keywords: antioxidant enzymes, bisphenol A, bisphenol a analogues, human erythrocytes

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Authors: Medina O. Kadiri, Jeffrey U. Ogbebor

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Toxin-producing algae are algal species that produce potent toxins, which accumulate in food chains and cause various gastrointestinal and neurological illnesses in humans and other animals. They result in shellfish toxicity, ecosystem alteration, cause fish kills and mortality of other animals and humans, in addition to compromised product quality as well as decreased consumer confidence. Animals, including man, are directly exposed to toxins by absorbing toxins from the water via swimming, drinking water with toxins, or ingestion of algal species via feeding on contaminated seafood. These toxins, algal toxins, undergo bioaccumulation, biotransformation, biotransferrence, and biomagnification through the natural food chains and food webs, thereby endangering animals and humans. The Nigerian coast is situated on the Atlantic Ocean, the Gulf of Guinea, one of Africa’s five large marine ecosystems (LME), and studies on toxic algae in this ecosystem are generally lacking. Algal samples were collected from eight coastal states and ten locations spanning the Bight of Bonny and the Bight of Benin. A total of 70 species of toxin-producing algae were found in the coastal waters of Nigeria. There was a great variety of toxin-producing algae in the coastal waters of Nigeria. They were Domoic acid-producing forms (DSP), Saxitoxin-producing, Gonyautoxin-producing, and Yessotoxin-producing (all PSP). Others were Okadaic acid-producing, Dinophysistoxin-producing, and Palytoxin-producing, which are representatives of DSP; CFP was represented by Ciguatoxin-producing forms and NSP by Brevitoxin-producing species. Emerging or new toxins are comprising of Gymnodimines, Spirolides, Palytoxins, and Prorocentrolidess-producing algae. The CyanoToxin Poisoning (CTP) was represented by Anatoxin-, Microcystin-, Cylindrospermopsis-Lyngbyatoxin-, Nordularin-Applyssiatoxin and Debromoapplatoxin-producing species. The highest group was the Saxitoxin-producing species, followed by Microcystin-producing species, then Anatoxin-producing species. Gonyautoxin (PSP), Palytoxin (DSP), Emerging toxins, and Cylindrospermopsin -producing species had a very substantial representation. Only Ciguatoxin-producing species, Lyngbyatoxin-Nordularin, Applyssiatoxin, and Debromoapplatoxin-producing species were represented by one taxon each. The presence of such overwhelming diversity of toxin-producing algae on the Nigerian coast is a source of concern for fisheries, aquaculture, human health, and ecosystem services. Therefore routine monitoring of toxic and harmful algae is greatly recommended.

Keywords: algal syndromes, Atlantic Ocean, harmful algae, Nigeria

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Authors: Syed Asif Hassan, Tabrej Khan

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Multiple sclerosis (MS) is a chronic demyelinating autoimmune disorder, of the central nervous system (CNS). In the present scenario, the current therapies either do not halt the progression of the disease or have side effects which limit the usage of current Disease Modifying Therapies (DMTs) for a longer period of time. Therefore, keeping the current treatment failure schema, we are focusing on screening novel analogues of the available DMTs that specifically bind and inhibit the Sphingosine1-phosphate receptor1 (S1PR1) thereby hindering the lymphocyte propagation toward CNS. The novel drug-like analogs molecule will decrease the frequency of relapses (recurrence of the symptoms associated with MS) with higher efficacy and lower toxicity to human system. In this study, an integrated approach involving ligand-based virtual screening protocol (Ultrafast Shape Recognition with CREDO Atom Types (USRCAT)) to identify the non-toxic drug like analogs of the approved DMTs were employed. The potency of the drug-like analog molecules to cross the Blood Brain Barrier (BBB) was estimated. Besides, molecular docking and simulation using Auto Dock Vina 1.1.2 and GOLD 3.01 were performed using the X-ray crystal structure of Mtb LprG protein to calculate the affinity and specificity of the analogs with the given LprG protein. The docking results were further confirmed by DSX (DrugScore eXtented), a robust program to evaluate the binding energy of ligands bound to the ligand binding domain of the Mtb LprG lipoprotein. The ligand, which has a higher hypothetical affinity, also has greater negative value. Further, the non-specific ligands were screened out using the structural filter proposed by Baell and Holloway. Based on the USRCAT, Lipinski’s values, toxicity and BBB analysis, the drug-like analogs of fingolimod and BG-12 showed that RTL and CHEMBL1771640, respectively are non-toxic and permeable to BBB. The successful docking and DSX analysis showed that RTL and CHEMBL1771640 could bind to the binding pocket of S1PR1 receptor protein of human with greater affinity than as compared to their parent compound (Fingolimod). In this study, we also found that all the drug-like analogs of the standard MS drugs passed the Bell and Holloway filter.

Keywords: antagonist, binding affinity, chemotherapeutics, drug-like, multiple sclerosis, S1PR1 receptor protein

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Authors: A. Lianah, B. Peter Sopade, C. Krisantini

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Walikadep/Tetrastigma glabratum (Blume) Planch is a traditional herb that has been used by people of Blumah village; it is believed to have a stimulant effect and ailments for many illnesses. Our survey demonstrated that the people of Blumah village has exploited walikadep from Protected Forest of Mount Prau. More than 10% of 448 households at Blumah village have used walikadep as traditional herb or jamu. Part of the walikadep plants used is the liquid extract of the stem. The population of walikadep is getting scarce and it is rarely found now. The objectives of this study are to examine the stimulant effect of walikadep, to measure growth and exploitation rate of walikadep, and to find ways to effectively propagate the plants, as well as identifying the impact on the environment through field experiments and explorative survey. Stimulant effect was tested using open-field and hole-board test. Data were collected through field observation and experiment, and data were analysed using lab test and Anova. Rate of exploitation and plant growth was measured using Regression analysis; comparison of plant growth in-situ and ex-situ used descriptive analysis. The environmental impact was measured by population structure vegetation analysis method by Shannon Weinner. The study revealed that the walikadep exudates did not have a stimulant effect. Exploitation of walikadep and the long time required to reach harvestable size resulted in the scarcity of the plant in the natural habitat. Plant growth was faster in-situ than ex-situ; and fast growth was obtained from middle part cuttings treated with vermicompost. Biodiversity index after exploitation was higher than before exploitation, possibly due to the toxic and allellopathic effect (phenolics) of the plant. Based on these findings, further research is needed to examine the toxic effects of the leave and stem extract of walikadep and their allelopathic effects. We recommend that people of Blumah village to stop using walikadep as the stimulant. The local people, village government in the regional and central levels, and perhutani should do an integrated efforts to conserve walikadep through Pengamanan Terpadu Konservasi Walikadep Lestari (PTKWL) program, so this population of this plant in the natural habitat can be maintained.

Keywords: utilization, medical plants, traditional, Tetastigma glabratum

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Authors: Karima Menad, Ahmed Feddag

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In this study, large crystals of the zeolite NaA were synthesized by hydrothermal way. By following this zeolite was used to recover two heavy metals that are allowing the most dangerous toxic, lead and cadmium. The synthesized zeolite was analyzed by XRD and SEM aims to verify its purity and its good morphology; after it was undergoing ion exchange operations by aqueous solution with lead and cadmium in two salts Pb(CH3COOH)2 and CdCl2 at different concentrations. The exchange was carried out under the effect of two temperatures (25 °C and 60 °C). The contents of Pb++, Cd++ and Na+ were analyzed by atomic absorption and the results are given in the form of exchange rates. At the end the samples are analyzed by XRD exchanged to confirm their conservation of their zeolite framework. It is found that the exchange rate increases with the increase of initial concentration and the best results are found for the temperature of 60 °C.

Keywords: exchange rate, ion exchange, LTA zeolite, zeolite NaA

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Authors: Bahaa Eldin A. Fouda, Khaled N. Yossef, Mohamed Elhosseny, Ahmed Lotfy, Mohamed Salama, Mohamed Sobh

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Developmental neurotoxicity (DNT) entails the toxic effects imparted by various chemicals on the brain during the early childhood period. As human brains are vulnerable during this period, various chemicals would have their maximum effects on brains during early childhood. Some toxicants have been confirmed to induce developmental toxic effects on CNS e.g. lead, however; most of the agents cannot be identified with certainty due the defective nature of predictive toxicology models used. A novel alternative method that can overcome most of the limitations of conventional techniques is the use of 3D neurospheres system. This in-vitro system can recapitulate most of the changes during the period of brain development making it an ideal model for predicting neurotoxic effects. In the present study, we verified the possible DNT of epoxomicin which is a naturally occurring selective proteasome inhibitor with anti-inflammatory activity. Rat neural progenitor cells were isolated from rat embryos (E14) extracted from placental tissue. The cortices were aseptically dissected out from the brains of the fetuses and the tissues were triturated by repeated passage through a fire-polished constricted Pasteur pipette. The dispersed tissues were allowed to settle for 3 min. The supernatant was, then, transferred to a fresh tube and centrifuged at 1,000 g for 5 min. The pellet was placed in Hank’s balanced salt solution cultured as free-floating neurospheres in proliferation medium. Two doses of epoxomicin (1µM and 10µM) were used in cultured neuropsheres for a period of 14 days. For proliferation analysis, spheres were cultured in proliferation medium. After 0, 4, 5, 11, and 14 days, sphere size was determined by software analyses. The diameter of each neurosphere was measured and exported to excel file further to statistical analysis. For viability analysis, trypsin-EDTA solution were added to neurospheres for 3 min to dissociate them into single cells suspension, then viability evaluated by the Trypan Blue exclusion test. Epoxomicin was found to affect proliferation and viability of neuropsheres, these effects were positively correlated to doses and progress of time. This study confirms the DNT effects of epoxomicin on 3D neurospheres model. The effects on proliferation suggest possible gross morphologic changes while the decrease in viability propose possible focal lesion on exposure to epoxomicin during early childhood.

Keywords: neural progentor cells, epoxomicin, neurosphere, medical and health sciences

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Authors: Hakima Althalb

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Petroleum contamination of sandy soils is a severe environmental problem in Libya, but relatively little work has been carried out to optimize the bioremediation of such heavily contaminated soil, particularly at a pilot scale. The purpose of this research was to determine the potential for the microbial-based bioremediation of hydrocarbon-contaminated soil obtained from an oil refinery in Libya and to assess the potential of both ozonation and phytoremediation (both applied after initial bioremediation) to reduce residual hydrocarbon levels. Plots containing 500 kg soil (triplicates) (contaminated soil diluted with clean soil 50% volume) were set up, (designated as Land Treatment Units; LTUs) containing five different nutrient levels and mixtures (Urea + NPK (nitrogen; phosphor; potassium) mixtures) to obtain C:N:P ratios 100:10:1, and monitored for 90 days. Hydrocarbon levels, microbial numbers, and toxicity (EC50 using luminescent microbial based tests) were assessed. Hydrocarbon levels in non-diluted and diluted soil ranged from 20 733-22 366 mg/kg and from 16 000-17 000 mg/kg respectively. Although all the land treatment units revealed a significant hydrocarbon reduction over time, the highest reduction in hydrocarbon levels obtained was around 60%. For example, 63% hydrocarbon removal was observed using a mixture of urea and NPK with a C:N:P ratio of 100:10:1). Soil toxicity (as assessed using luminescence based toxicity assays) reduced in line with the reduction in total petroleum hydrocarbons observed. However, as relatively high residual TPH (total petroleum hydrocarbon) levels (ranging from 6033-14166mg/kg) were still present after initial bioremediation two ‘post-treatments’ (phytoremediation and ozonation) were attempted to remove residual hydrocarbons remaining. Five locally grown (agriculturally important) plant species were tested. The germination of all plants examined was strongly inhibited (80-100%) and seedlings failed to grow well in the contaminated soil, indicating that the previously bioremediated soils were still toxic to the plants. Subsequent ozonation followed by another bioremediation of soil was more successful than phytoremediation. But even the most promising successful treatment in this study (ozonation for 6 hours at 25ppm followed by bioremediation) still only removed approximately 31% of the residual hydrocarbons. Overall, this work showed that the bioremediation of such highly contaminated soils is difficult and that a combination of treatments would be required to achieve successful remediation. Even after initial dilution and bioremediation the soils remained toxic to plant growth and were therefore not suitable for phytoremediation.

Keywords: bioremediation, petroleum hydrocarbons, ozone, phytoremediation

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Authors: Harish Kuruva, Vedasri Bai Khavala, Tiju Thomas, K. Murugan, B. S. Murty

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Industries are growing day to day to increase the economy of the country. The biggest problem with industries is wastewater treatment. Releasing these wastewater directly into the river is more harmful to human life and a threat to aquatic life. These industrial effluents contain many dissolved solids, organic/inorganic compounds, salts, toxic metals, etc. Phenols, pesticides, dioxins, herbicides, pharmaceuticals, and textile dyes were the types of industrial effluents and more challenging to degrade eco-friendly. So many advanced techniques like electrochemical, oxidation process, and valorization have been applied for industrial wastewater treatment, but these are not cost-effective. Industrial effluent degradation is complicated compared to commercially available pollutants (dyes) like methylene blue, methylene orange, rhodamine B, etc. TiO₂ is one of the widely used photocatalysts which can degrade organic compounds using solar light and moisture available in the environment (organic compounds converted to CO₂ and H₂O). TiO₂ is widely studied in photocatalysis because of its low cost, non-toxic, high availability, and chemically and physically stable in the atmosphere. This study mainly focused on valorizing the mineralogical product TiO₂ (IREL, India). This mineralogical graded TiO₂ was characterized and compared with its structural and photocatalytic properties (industrial effluent degradation) with the commercially available Degussa P-25 TiO₂. It was testified that this mineralogical TiO₂ has the best photocatalytic properties (particle shape - spherical, size - 30±5 nm, surface area - 98.19 m²/g, bandgap - 3.2 eV, phase - 95% anatase, and 5% rutile). The industrial effluent was characterized by TDS (total dissolved solids), ICP-OES (inductively coupled plasma – optical emission spectroscopy), CHNS (Carbon, Hydrogen, Nitrogen, and sulfur) analyzer, and FT-IR (fourier-transform infrared spectroscopy). It was observed that it contains high sulfur (S=11.37±0.15%), organic compounds (C=4±0.1%, H=70.25±0.1%, N=10±0.1%), heavy metals, and other dissolved solids (60 g/L). However, the organo-sulfur industrial effluent was degraded by photocatalysis with the industrial mineralogical product TiO₂. In this study, the industrial effluent pH value (2.5 to 10), catalyst concentration (50 to 150 mg) were varied, and effluent concentration (0.5 Abs) and light exposure time (2 h) were maintained constant. The best degradation is about 80% of industrial effluent was achieved at pH 5 with a concentration of 150 mg - TiO₂. The FT-IR results and CHNS analyzer confirmed that the sulfur and organic compounds were degraded.

Keywords: wastewater treatment, industrial mineralogical product TiO₂, photocatalysis, organo-sulfur industrial effluent

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Authors: Elise M. Shauf

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Beryllium can be found naturally in some fruits and vegetables (carrots, garden peas, kidney beans, pears) at very low concentrations, but is typically not clinically significant due to the low-level exposure and limited absorption of beryllium by the stomach and intestines. However, acute or chronic beryllium exposure can result in harmful toxic and carcinogenic biological effects. Beryllium can be both a workplace hazard and an environmental pollutant, therefore determining the presence of beryllium at trace levels can be essential to protect workers as well as the environment. Analysis of gallein, C₂₀H₁₂O₇, to determine if it is usable as a fluorescent dye for beryllium detection. The primary detection method currently in use includes hydroxybenzoquinoline sulfonates (HBQS), for which alternative indicators are desired. Unfortunately, gallein does not have the desired aspects needed as a dye for beryllium detection due to the peak shift properties.

Keywords: beryllium detection, fluorescent, gallein dye, indicator, spectroscopy

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Authors: D. Malouch, M. Berchel, C. Dreanno, S. Stachowski-Haberkorn, P-A. Jaffres

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Biofilm is a predominant lifestyle chosen by bacteria. Whether it is developed on an immerged surface or a mobile biofilm known as flocs, the bacteria within this form of life show properties different from its planktonic ones. Within the biofilm, the self-formed matrix of Extracellular Polymeric Substances (EPS) offers hydration, resources capture, enhanced resistance to antimicrobial agents, and allows cell-communication. Biofouling is a complex natural phenomenon that involves biological, physical and chemical properties related to the environment, the submerged surface and the living organisms involved. Bio-colonization of artificial structures can cause various economic and environmental impacts. The increase in costs associated with the over-consumption of fuel from biocolonized vessels has been widely studied. Measurement drifts from submerged sensors, as well as obstructions in heat exchangers, and deterioration of offshore structures are major difficulties that industries are dealing with. Therefore, surfaces that inhibit biocolonization are required in different areas (water treatment, marine paints, etc.) and many efforts have been devoted to produce efficient and eco-compatible antifouling agents. The different steps of surface fouling are widely described in literature. Studying the biofilm and its stages provides a better understanding of how to elaborate more efficient antifouling strategies. Several approaches are currently applied, such as the use of biocide anti-fouling paint6 (mainly with copper derivatives) and super-hydrophobic coatings. While these two processes are proving to be the most effective, they are not entirely satisfactory, especially in a context of a changing legislation. Nowadays, the challenge is to prevent biofouling with non-biocide compounds, offering a cost effective solution, but with no toxic effects on marine organisms. Since the micro-fouling phase plays an important role in the regulation of the following steps of biofilm formation7, it is desired to reduce or delate biofouling of a given surface by inhibiting the micro fouling at its early stages. In our recent works, we reported that some amphiphilic compounds exhibited bacteriostatic or bactericidal properties at a concentration that did not affect eukaryotic cells. These remarkable properties invited us to assess this type of bio-inspired phospholipids9 to prevent the colonization of surfaces by marine bacteria. Of note, other studies reported that amphiphilic compounds interacted with bacteria leading to a reduction of their development. An amphiphilic compound is a molecule consisting of a hydrophobic domain and a polar head (ionic or non-ionic). These compounds appear to have interesting antifouling properties: some ionic compounds have shown antimicrobial activity, and zwitterions can reduce nonspecific adsorption of proteins. Herein, we investigate the potential of amphiphilic compounds as inhibitors of bacterial growth and marine biofilm formation. The aim of this study is to compare the efficacy of four synthetic phospholipids that features a cationic charge (BSV36, KLN47) or a zwitterionic polar-head group (SL386, MB2871) to prevent microfouling with marine bacteria. We also study the toxicity of these compounds in order to identify the most promising compound that must feature high anti-adhesive properties and a low cytotoxicity on two links representative of coastal marine food webs: phytoplankton and oyster larvae.

Keywords: amphiphilic phospholipids, bacterial biofilm, marine microfouling, non-toxic antifouling

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Authors: Dmitriy Berillo, Areej K. A. Al-Jwaid, Jonathan L. Caplin, Andrew Cundy, Irina Savina

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Chlorophenols (CPs) are used as a precursor in the production of higher CPs and dyestuffs, and as a preservative. Contamination by CPs of the ground water is located in the range from 0.15-100mg/L. The EU has set maximum concentration limits for pesticides and their degradation products of 0.1μg/L and 0.5μg/L, respectively. People working in industries which produce textiles, leather products, domestic preservatives, and petrochemicals are most heavily exposed to CPs. The International Agency for Research on Cancers categorized CPs as potential human carcinogens. Existing multistep water purification processes for CPs such as hydrogenation, ion exchange, liquid-liquid extraction, adsorption by activated carbon, forward and inverse osmosis, electrolysis, sonochemistry, UV irradiation, and chemical oxidation are not always cost effective and can cause the formation of even more toxic or mutagenic derivatives. Bioremediation of CPs derivatives utilizing microorganisms results in 60 to 100% decontamination efficiency and the process is more environmentally-friendly compared with existing physico-chemical methods. Microorganisms immobilized onto a substrate show many advantages over free bacteria systems, such as higher biomass density, higher metabolic activity, and resistance to toxic chemicals. They also enable continuous operation, avoiding the requirement for biomass-liquid separation. The immobilized bacteria can be reused several times, which opens the opportunity for developing cost-effective processes for wastewater treatment. In this study, we develop a bioremediation system for CPs based on macroporous materials, which can be efficiently used for wastewater treatment. Conditions for the preparation of the macroporous material from specific bacterial strains (Pseudomonas mendocina and Rhodococus koreensis) were optimized. The concentration of bacterial cells was kept constant; the difference was only the type of cross-linking agents used e.g. glutaraldehyde, novel polymers, which were utilized at concentrations of 0.5 to 1.5%. SEM images and rheology analysis of the material indicated a monolithic macroporous structure. Phenol was chosen as a model system to optimize the function of the cryogel material and to estimate its enzymatic activity, since it is relatively less toxic and harmful compared to CPs. Several types of macroporous systems comprising live bacteria were prepared. The viability of the cross-linked bacteria was checked using Live/Dead BacLight kit and Laser Scanning Confocal Microscopy, which revealed the presence of viable bacteria with the novel cross-linkers, whereas the control material cross-linked with glutaraldehyde(GA), contained mostly dead cells. The bioreactors based on bacteria were used for phenol degradation in batch mode at an initial concentration of 50mg/L, pH 7.5 and a temperature of 30°C. Bacterial strains cross-linked with GA showed insignificant ability to degrade phenol and for one week only, but a combination of cross-linking agents illustrated higher stability, viability and the possibility to be reused for at least five weeks. Furthermore, conditions for CPs degradation will be optimized, and the chlorophenol degradation rates will be compared to those for phenol. This is a cutting-edge bioremediation approach, which allows the purification of waste water from sustainable compounds without a separation step to remove free planktonic bacteria. Acknowledgments: Dr. Berillo D. A. is very grateful to Individual Fellowship Marie Curie Program for funding of the research.

Keywords: bioremediation, cross-linking agents, cross-linked microbial cell, chlorophenol degradation

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Authors: Serpil Kilic, Ihsan Burak Cam, Murat Kilic, Timur Tongur

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Interest in the lead (Pb) has considerably increased due to knowledge about the potential toxic effects of this element, recently. Exposure to heavy metals above the acceptable limit affects human health. Indeed, Pb is accumulated through food chains up to toxic concentrations; therefore, it can pose an adverse potential threat to human health. A sensitive and reliable method for determination of Pb element in red pepper were improved in the present study. Samples (33 red pepper products having different brands) were purchased from different markets in Turkey. The selected method validation criteria (linearity, Limit of Detection, Limit of Quantification, recovery, and trueness) demonstrated. Recovery values close to 100% showed adequate precision and accuracy for analysis. According to the results of red pepper analysis, all of the tested lead element in the samples was determined at various concentrations. A Perkin- Elmer ELAN DRC-e model ICP-MS system was used for detection of Pb. Organic red pepper was used to obtain a matrix for all method validation studies. The certified reference material, Fapas chili powder, was digested and analyzed, together with the different sample batches. Three replicates from each sample were digested and analyzed. The results of the exposure levels of the elements were discussed considering the scientific opinions of the European Food Safety Authority (EFSA), which is the European Union’s (EU) risk assessment source associated with food safety. The Target Hazard Quotient (THQ) was described by the United States Environmental Protection Agency (USEPA) for the calculation of potential health risks associated with long-term exposure to chemical pollutants. THQ value contains intake of elements, exposure frequency and duration, body weight and the oral reference dose (RfD). If the THQ value is lower than one, it means that the exposed population is assumed to be safe and 1 < THQ < 5 means that the exposed population is in a level of concern interval. In this study, the THQ of Pb was obtained as < 1. The results of THQ calculations showed that the values were below one for all the tested, meaning the samples did not pose a health risk to the local population. This work was supported by The Scientific Research Projects Coordination Unit of Akdeniz University. Project Number: FBA-2017-2494.

Keywords: lead analyses, red pepper, risk assessment, daily exposure

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Authors: M. R. Bindhu, M. Umadevi

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Silver nanoparticles have been synthesized by Daucus carota extract as reducing agent was reported here. The involvement of phytochemicals in the Daucus carota extract in the reduction and stabilization of silver nanoparticles has been established using XRD and UV-vis studies. The UV-vis spectrum of the prepared silver nanoparticles showed surface plasmon absorbance peak at 450 nm. The obtained silver nanoparticles were almost spherical in shape with the average size of 15 nm. Crystalline nature of the nanoparticles was evident from bright spots in the SAED pattern and peaks in the XRD pattern. This new, simple and natural method for biosynthesis of silver nanoparticles offers a valuable contribution in the area of green synthesis and nanotechnology avoiding the presence of hazardous and toxic solvents and waste.

Keywords: Daucus carota, green synthesis, silver nanoparticles, surface plasmon resonance

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Authors: Chro Kawyan

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Endothelin-1 (ET-1), the principal individual from the newfound mammalian endothelin group of organically dynamic peptides, was initially distinguished as a 21 buildup powerful vasoconstrictor peptide in vascular endothelial cells. However, it has since been demonstrated to have a wide range of pharmacological activities in tissues both inside and outside the cardiovascular system. Additionally, peptides that have a striking resemblance to ET-1 have been identified as the primary toxic component of snake venom. In addition, late examinations have proposed that warm blooded creatures, including people, produce three unmistakable individuals from this peptide family, ET-1, ET-2 and ET-J, which might have various profiles of organic action and may follow up on particular subtypes of endothelin receptor. Masashi Yanagisawa and Tomoh Masaki survey the ongoing status of the organic chemistry and sub-atomic science of endothelin.

Keywords: thelin, microbiology, molecular biology, cell

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Authors: D. ChobfroushKhoei, S. K. Heidari , Sh. Dariadel

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Carbon nanotubes were used in medical sciences especially in drug delivery system and cancer therapy. In this study, we functionalized carboxylated single-wall carbon nanotubes (SWNT-COOH) with 2-en 4-hydroxy cyclo 1-octanon. Synthesized sample was characterized by FT-IR, Raman spectroscopy, SEM, TGA and cellular investigations. The results showed well formation of SWNT-Ester. Cell viability assay results and microscopic observations demonstrated that cancerous cells were killed in the sample. The synthesized sample can be used as a toxic material for cancer therapy.

Keywords: MWNT-COOH, functionalization, phenylisocyanate, phenylisothiocyanate, 1, 4-phenylendiamine, toxicity investigation

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Authors: Thapelo Aubrey Motsieng

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Fluidized bed combustion (FBC) is a clean coal technology used in the combustion of low-grade coals for power generation. The production of large solid wastes such as bottom ashes from this process is a problem. The bottom ash contains some toxic elements which can leach out soils and contaminate surface and ground water; for this reason, they can neither be disposed of in landfills nor lagoons anymore. The production of geopolymers from bottom ash for structural and concrete applications is an option for their disposal. In this study, the waste bottom ash obtained from the combustion of three low grade South African coals in a bubbling fluidized bed reactor was used to produce geopolymers. The geopolymers were cured in a household microwave. The results showed that the microwave curing enhanced the reactivity and strength of the geopolymers.

Keywords: bottom ash, geopolymers, coal, compressive strength

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Authors: F. Garousi, S. Veres, É. Bódi, S. Várallyay, B. Kovács

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Extracting and determining chlorophyll pigments (chlorophyll a and b) in green leaves are the procedures based on the solvent extraction of pigments in samples using N,N-dimethylformamide as the extractant. In this study, two species of soluble inorganic selenium forms, selenite (Se( IV)) and selenate (Se( VI)) at different concentrations were investigated on maize plants that were growing in nutrient solutions during 2 weeks and at the end of the experiment, amounts of chlorophyll a and b for first and second leaves of maize were measured. In accordance with the results we observed that our regarded Se concentrations in both forms of Se( IV) and Se( VI) were not effective on maize plants’ chlorophyll a and b significantly although high level of 3 mg.kg-1 Se( IV) had negative affect on growth of the samples that had been treated by it but about Se( VI) samples we did not observe this state and our different considered Se( VI) concentrations were not toxic for maize plants.

Keywords: maize, sodium selenate, sodium selenite, chlorophyll a and b

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Authors: Mohamed El-Bady

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The Northern Egyptian Lagoons are (from east to west) Bardawil Lagoon, Manzala Lagoon, Burullus Lagoon, Edku Lagoons and Mariute Lagoon. These lagoons have been received the bulk of drainage water from the lands of Delta and from the other coastal areas. Where, the heavy metals can occur in Lagoons environments through a variety of sources, including industries, wastewaters and domestic effluents. The potential ecological risk index (RI) calculation of the bottom sediments of the northern lagoons depends on contamination factor (CF), potential ecological risk factor and proposed toxic response factor (Tr). Each lagoon with special indices according to its conditions.

Keywords: Northern Lagoons, Nile Delta, ecological risk index, contamination factor

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Authors: K. Menad, A. Faddeg

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Zeolites are a family of mineral compounds. With special properties that have led to several important industrial applications. Ion exchange has enabled the first industrial application in the field of water treatment. The exchange by aqueous pathway is the method most used in the case of such microporous materials and this technique will be used in this work. The objective of this work is to find performance materials for the recovery of heavy metals such as cadmium. The study is to compare the properties of different ion exchange zeolite Na-X, Na-A, their physical mixture and the composite A (LTA) / X (FAU). After the synthesis of various zeolites X and A, it was designed a model Core-Shell to form a composite zeolite A on zeolite X. Finally, ion exchange studies were performed on these zeolite materials. The cation is exclusively tested for cadmium, a toxic element and is harmful to health and the environment.

Keywords: zeolite A, zeolite X, ion exchange, water treatment

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Authors: Ayse Arslan

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One of the important elements underpinning a conscious design is the degree of toxicity in communication. This study explores the mechanisms and strategies for identifying toxic content by avoiding dark patterns. Given the breadth of hate and harassment attacks, this study explores a threat model and taxonomy to assist in reasoning about strategies for detection, prevention, mitigation, and recovery. In addition to identifying some relevant techniques such as nudges, automatic detection, or human-ranking, the study suggests the use of major metrics such as the overhead and friction of solutions on platforms and users or balancing false positives (e.g., incorrectly penalizing legitimate users) against false negatives (e.g., users exposed to hate and harassment) to maintain a conscious design towards fairness.

Keywords: AI, ML, algorithms, policy, system design

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Authors: Ali Akrmi, Mohamed Beji, Ahmed Baklouti, Fatma Djouani, Philippe Lang, Mohamed M. Chehimi

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Poly(vinyl chloride) (PVC) is a highly versatile polymer with excellent balance of properties and numerous applications such as water pipes, packaging and polymer materials of importance in the biomedical sector. However, depending on the applications, it is necessary to modify PVC by mixing with a plasticizer; surface modification using plasma, surface grafting or flame treatment; or bulk chemical modification which affects the entire PVC chains at an extent that can be tuned by the polymer chemist. The targeted applications are improvement of chemical resistance, avoiding or limitation of migration of toxic plasticizers, improvement of antibacterial properties, or control of blood compatibility.

Keywords: poly(vinyl chloride), nucleophilic substitution, sulfonylcarbamates, XPS

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Authors: Hamid Abdulroof Saleh

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Background: Dioxins are one of the most widely distributed environmental pollutants. Dioxins consist of feedstock during the preparation of some industries, such as the paper industry as they can be produced in the atmosphere during the process of burning garbage and waste, especially medical waste. Dioxins can be found in the adipose tissues of animals in the food chain as well as in human breast milk. 2,3,7,8-Tetrachlorodibenzo-pdioxin (TCDD) is the most toxic component of a large group of dioxins. Humans are exposed to TCDD through contaminated food items like meat, fish, milk products, eggs etc. Recently, natural formulations relating to reducing or eliminating TCDD toxicity have been in focus. Ginger rhizome (Zingiber officinale R., family: Zingiberaceae), is used worldwide as a spice. Both antioxidative and androgenic activity of Z. officinale was reported in animal models. Researchers showed that ginger oil has dominative protective effect on DNA damage and might act as a scavenger of oxygen radical and might be used as an antioxidant. Aim of the work: The present study was undertaken to evaluate the toxic effect of TCDD on the structure and histoarchitecture of the testis and the protective role of co-administration of ginger root extract to prevent this toxicity. Materials & Methods: Male adult rats of Sprague-Dawley strain were assigned to four groups, eight rats in each; control group, dioxin treated group (given TCDD at the dose of 100 ng/kg Bwt/day by gavage), ginger treated group (given 50 mg/kg Bwt/day of ginger root extract by gavage), dioxin and ginger treated group (given TCDD at the dose of 100 ng/kg Bwt/day and 50 mg/kg Bwt/day of ginger root extract by gavages). After three weeks, rats were weighed and sacrificed where testis were removed and weighted. The testes were processed for routine paraffin embedding and staining. Tissue sections were examined for different morphometric and histopathological changes. Results: Dioxin administration showed a harmful effects in the body, testis weight and other morphometric parameters of the testis. In addition, it produced varying degrees of damage to the seminiferous tubules, which were shrunken and devoid of mature spermatids. The basement membrane was disorganized with vacuolization and loss of germinal cells. The co-administration of ginger root extract showed obvious improvement in the above changes and showed reversible morphometric and histopathological changes of the seminiferous tubules. Conclusion: Ginger root extract treatment in this study was successful in reversing all morphometric and histological changes of dioxin testicular damage. Therefore, it showed a protective effect on testis against dioxin toxicity.

Keywords: dioxin, ginger, rat, testis

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Authors: Deepali Lal, Sudha Summerwar, Jyoutsna Pandey

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The resistance of pesticide by the pest is an important matter of concern.The pesticide of plant origin having nontoxic biodegradable and environmentally friendly qualities. The frequent spraying of toxic chemicals is developing resistance to the pesticide. Leaf powder of the plants like Argimone mexicana and Calotropis procera is prepared, Different doses of these plant extracts are given to the Fourth in star stages of Helicoverpa armigera through feeding methods, to find their efficacy the experimental findings will be put under analysis using various parameters. The effect on paritrophic membrane is also studied.

Keywords: distillation plant, acetone, alcohol, pipette, castor leaves, grams pods, larvae of helicoverpa armigera, plant extract, vails, jars, cotton

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Authors: Vandana Deopanée Tomar, Gurpreet Kaur Sidhu, Panchsheela Nogia, Rajesh Mehrotra, Sandhya Mehrotra

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The cyanobacterial CO₂ concentrating mechanism (CCM) operates to raise the levels of CO₂ in the vicinity of the main carboxylation enzyme Rubisco which is encapsulated in protein micro compartments called carboxysomes. Thus, due to the presence of CCM, cyanobacterial cells are able to work with high photosynthetic efficiency even at low Ci conditions and can accumulate 1000 folds high internal concentrations of Ci than external environment. Engineering of some useful CCM components into higher plants is one of the plausible approaches to improve their photosynthetic performance. The first step and the simplest approach for attaining this objective would be the transfer of cyanobacterial bicarbonate transporter such as SbtA to inner chloroplast envelope of C₃ plants. For this, SbtA transporter gene from Synechococcus elongatus PCC 7942 was fused to a transit peptide element to generate chimeric constructs in order to direct it to chloroplast inner envelope. Two transit peptides namely, TnaXTP (transit peptide from AT3G56160) and TMDTP (transit peptide from AT2G02590) were shortlisted from Arabidopsis thaliana genome and cloned in plant expression vector pCAMBIA1302 having mgfp5 as a reporter gene. Plant transformation was done by agro infiltration and Agrobacterium mediated co-culture. DNA, RNA, and protein were isolated from the leaves four days post infiltration, and the presence of transgene was confirmed by gene specific PCR (Polymerase Chain Reaction) analysis and by RT-PCR (Reverse Transcription Polymerase Chain Reaction). The expression was confirmed at the protein level by western blotting using anti-GFP primary antibody and horseradish peroxidase (HRP) conjugated secondary antibody. The localization of the protein was detected by confocal microscopy of isolated protoplasts. We observed chloroplastic expression for both the fusion constructs which suggest that the transit peptide sequences are capable of taking the cargo protein to the chloroplasts. These constructs are now being used to generate stable transgenic plants by Agrobacterium mediated transformation. The stability of transgene expression will be analyzed from T₀ to T₂ generation.

Keywords: agro infiltration, bicarbonate transporter, carbon concentrating mechanisms, cyanobacteria, SbtA

Procedia PDF Downloads 192

Authors: M. Černe, I. Palčić, D. Anđelini, D. Cvitan, N. Major, M. Lukić, S. Goreta Ban, D. Ban, T. Rijavec, A. Lapanje

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Context: In the Mediterranean basin, large quantities of lignocellulosic by-products, such as olive pomace (OP), are generated during olive processing on an annual basis. Due to the phytotoxic nature of OP, composting is recommended for its stabilisation to produce the end-product safe for agricultural use. Research Aim: This study aims to evaluate the applicability of olive pomace compost (OPC) for use as a soil amendment by considering its physical and chemical characteristics and microbiological parameters. Methodology: The OPC samples were collected from the surface and depth layers of the compost pile after 8 months. The samples were analyzed for their C/N, pH, EC, total phenolic content, residual oils, and elemental content, as well as colloidal properties and microbial community structure. The specific analytical approaches used are detailed in the poster. Findings: The results showed that the pH of OPC ranged from 7.8 to 8.6, while the electrical conductivity was from 770 to 1608 mS/cm. The levels of nitrogen (N), phosphorus (P), and potassium (K) varied within the ranges of 1.5 to 27.2 g/kg d.w., 1.6 to 1.8 g/kg d.w., and 6.5 to 7.5 g/kg d.w., respectively. The contents of potentially toxic metals such as chromium (Cr), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) were below the EU limits for soil improvers. The microbial structure follows the changes of the gradient from the outer to the innermost layer with relatively low amounts of DNA. The gradient nature shows that it is needed to develop better strategies for composting surpassing the conventional approach. However, the low amounts of total phenols and oil residues indicated efficient biodegradation during composting. The carbon-to-nitrogen ratio (C/N) within the range of 13 to 16 suggested that OPC can be used as a soil amendment. Overall, the study suggests that composting can be a promising strategy for environmentally-friendly OP recycling. Theoretical Importance: This study contributes to the understanding of the use of OPC as a soil amendment and its potential benefits in resource recycling and reducing environmental burdens. It also highlights the need for improved composting strategies to optimize its process. Data Collection and Analysis Procedures: The OPC samples were taken from the compost pile and charasterised for selected chemical, physical and microbial parameters. The specific analytical procedures utilized are described in detail in the poster. Question Addressed: This study addresses the question of whether composting can be optimized to improve the biodegradation of OP. Conclusion: The study concludes that OPC has the potential to be used as a soil amendment due to its favorable physical and chemical characteristics, low levels of potentially toxic metals, and efficient biodegradation during composting. However, the results also suggest the need for improved composting strategies to improve the quality of OPC.

Keywords: olive pomace compost, waste valorisation, agricultural use, soil amendment

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Authors: Osholana Tobi Stephen, Rotimi Emmanuel Sadiku, Bilainu Oboirien.o

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Fluidized bed combustion (FBC) is a clean coal technology used in the combustion of low-grade coals for power generation. The production of large solid wastes such as bottom ashes from this process is a problem. The bottom ash contains some toxic elements which can leach out soils and contaminate surface and ground water; for this reason, they can neither be disposed in landfills nor lagoons anymore. The production of geopolymers from bottom ash for structural and concrete applications is an option for their disposal. In this study, the waste bottom ash obtained from the combustion of three low grade South African coals in a bubbling fluidized bed reactor was used to produce geopolymers. The geopolymers were cured in a household microwave. The results showed that the microwave curing enhanced the reactivity and strength of the geopolymers.

Keywords: bottom ash, coal, fluidized bed combustion (FBC) geopolymer, compressive strength

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Authors: Anna Wolowicz, Katarzyna Staszak, Zbigniew Hubicki

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Nowadays heavy metal ions as well as surfactants are widely used throughout the world due to their useful properties. The consequence of such widespread use is their significant production. On the other hand, the increasing demand for surfactants and heavy metal ions results in production of large amounts of wastewaters which are discharged to the environment from mining, metal plating, pharmaceutical, cosmetic, fertilizer, paper, pesticide and electronic industries, pigments producing, petroleum refining and from autocatalyst, fibers, food, polymer industries etc. Heavy metal ions are non-biodegradable in the environment, cable of accumulation in living organisms and organs, toxic and carcinogenic. On the other hand, not only heavy metal ions but also surfactants affect the purity of water and soils. Some of surfactants are also toxic, harmful and dangerous because they are able to penetrate into surface waters causing foaming, blocked diffusion of oxygen from the atmosphere and act as emulsifiers of hydrophobic substances and increase solubility of many the dangerous pollutants. Among surfactants the anionic ones dominate and their share in the global production of surfactants is around 50 ÷ 60%. Due to the negative impact of heavy metals and surfactants on aquatic ecosystems and living organisms, removal and monitoring of their concentration in the environment is extremely important. Surfactants and heavy metal ions removal can be achieved by different biological and physicochemical methods. The adsorption as well as the ion-exchange methods play here a significant role. The aim of this study was heavy metal ions removal from aqueous solutions using different types of ion exchangers in the presence of anionic surfactants. Preliminary studies of copper(II), nickel(II), zinc(II) and cobalt(II) removal from acidic solutions using ion exchangers (Lewatit MonoPlus TP 220, Lewatit MonoPlus SR 7, Purolite A 400 TL, Purolite A 830, Purolite S 984, Dowex PSR 2, Dowex PSR3, Lewatit AF-5) allowed to select the most effective ones for the above mentioned sorbates and then to checking their removal efficiency in the presence of anionic surfactants. As it was found out Lewatit MonoPlus TP 220 of the chelating type, show the highest sorption capacities for copper(II) ions in comparison with the other ion exchangers under discussion, e.g. 9.98 mg/g (0.1 M HCl); 9.12 mg/g (6 M HCl). Moreover, cobalt(II) removal efficiency was the highest in 0.1 M HCl using also Lewatit MonoPlus TP 220 (6.9 mg/g) similar to zinc(II) (9.1 mg/g) and nickiel(II) (6.2 mg/g). As the anionic surfactant sodium dodecyl sulphate (SDS) was used and surfactant parameters such as viscosity (η), density (ρ) and critical micelle concentration (CMC) were obtained: η = 1.13 ± 0,01 mPa·s; ρ = 999.76 mg/cm3; CMC = 2.26 g/cm3. The studies of copper(II) removal from acidic solutions in the presence of SDS of different concentration show negligible effects on copper(II) removal efficiency. The sorption capacity of Cu(II) from 0.1 M acidic solution of 500 mg/L initial concentration was equal to 46.8 mg/g whereas in the presence of SDS 45.3 mg/g (0.1 mg SDS/L), 47.1 mg/g (0.5 mg SDS/L), 46.6 mg/g (1 mg SDS/L).

Keywords: anionic surfactant, heavy metal ions, ion exchanger, removal

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Authors: Mohammed Fathima Shahanaaz, Shaik Fayazuddin, M. Uday Kiran

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Groundwater quality is deteriorating day by day in different parts of the world due to various reasons, toxic chemicals are being discharged without proper treatment into inland water bodies and land which in turn add pollutants to the groundwater. In this kind of situation, the rural communities which do not have municipal drinking water have to rely on groundwater though it is polluted for various uses. Tannery industry is one of the major industry which provides economy and employment to India. Since most of the developed countries stopped using chemicals which are toxic, the tanning industry which uses chromium as its major element are being shifted towards developing countries. Most of the tanning industries in India can be found in clusters concentrated mainly in states of Tamilnadu, West Bengal, Uttar Pradesh and limited places of Punjab. Limited work is present in the case of tanneries of Warangal. There exists 18 group of tanneries in Desaipet, Enamamula region of Warangal, out of which 4 are involved in dry process and are low responsible for groundwater pollution. These units of tanneries are discharging their effluents after treatment into Sai Cheruvu. Though the treatment effluents are being discharged, the Sai Cheruvu is turned in to Pink colour, with higher levels of BOD, COD, chromium, chlorides, total hardness, TDS and sulphates. An attempt was made to analyse the groundwater samples around this polluted Sai Cheruvu region since literature shows that a single tannery can pollute groundwater to a radius of 7-8 kms from the point of disposal. Sample are collected from 6 different locations around Sai Cheruvu. Analysis was performed for determining various constituents in groundwater such as pH, EC, TDS, TH, Ca+2, Mg+2, HCO3-, Na+, K+, Cl-, SO42-, NO3-, F and Cr+6. The analysis of these constitutes gave values greater than permissible limits. Even chromium is also present in groundwater samples which is exceeding permissible limits People in Paidepally and Sardharpeta villages already stopped the usage of groundwater. They are buying bottle water for drinking purpose. Though they are not using groundwater for drinking purpose complaints are made about using this water for washing also. So treatment process should be adopted for groundwater which should be simple and efficient. In this study rice husk silica (RHS) is used to treat pollutants in groundwater with varying dosages of RHS and contact time. Rice husk is treated, dried and place in a muffle furnace for 6 hours at 650°C. Reduction is observed in total hardness, chlorides and chromium levels are observed after the application RHS. Pollutants reached permissible limits for 27.5mg/l and 50 mg/l of dosage for a contact time of 130 min at constant pH and temperature.

Keywords: chromium, groundwater, rice husk silica, tanning industries

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Authors: Michelle Blewitt, Scott P. Wilson, Heidi Tait, Juniper Riordan

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Rubber crumb is a physical and chemical pollutant of concern for the environment and human health, warranting immediate investigations into its pathways to the environment and potential impacts. This emerging microplastic is created by shredding end-of-life tyres into ‘rubber crumb’ particles between 1-5mm used on synthetic turf fields and soft-fall playgrounds as a solution to intensifying tyre waste worldwide. Despite having known toxic and carcinogenic properties, studies into the transportation pathways and movement patterns of rubber crumbs from these surfaces remain in their infancy. To address this deficit, AUSMAP, the Australian Microplastic Assessment Project, in partnership with the Tangaroa Blue Foundation, conducted a study to quantify crumb loss from soft-fall surfaces. To our best knowledge, this is the first of its kind, with funding for the audits being provided by the Australian Government’s Reef Trust. Sampling occurred at 12 soft-fall playgrounds within the Great Barrier Reef Catchment Area on Australia’s North-East coast, in close proximity to the United Nations World Heritage Listed Reef. Samples were collected over a 12-month period using randomized sediment cores at 0, 2 and 4 meters away from the playground edge along a 20-meter transect. This approach facilitated two objectives pertaining to particle movement: to establish that crumb loss is occurring and that it decreases with distance from the soft-fall surface. Rubber crumb abundance was expressed as a total value and used to determine an expected average of rubber crumb loss per m2. An Analysis of Variance (ANOVA) was used to compare the differences in crumb abundance at each interval from the playground. Site characteristics, including surrounding sediment type, playground age, degree of ultra-violet exposure and amount of foot traffic, were additionally recorded for the comparison. Preliminary findings indicate that crumb is being lost at considerable rates from soft-fall playgrounds in the region, emphasizing an urgent need to further examine it as a potential source of aquatic pollution, soil contamination and threat to individuals who regularly utilize these surfaces. Additional implications for the future of rubber crumbs as a fit-for-purpose recycling initiative will be discussed with regard to industry, governments and the economic burden of surface maintenance and/ or replacement.

Keywords: microplastics, toxic rubber crumb, litter pathways, marine environment

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Authors: I. Berger, N. Machour, F. Portet-Koltalo

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Polycyclic aromatic hydrocarbons (PAHs) are toxic and carcinogenic pollutants produced in majority by incomplete combustion processes in industrialized and urbanized areas. After being emitted in atmosphere, these persistent contaminants are deposited to soils or sediments. Even if persistent, some can be partially degraded (photodegradation, biodegradation, chemical oxidation) and they lead to oxygenated metabolites (oxy-PAHs) which can be more toxic than their parent PAH. Oxy-PAHs are less measured than PAHs in sediments and this study aims to compare different analytical tools in order to extract and quantify a mixture of four hydroxylated PAHs (OH-PAHs) and four carbonyl PAHs (quinones) in sediments. Methodologies: Two analytical systems – HPLC with on-line UV and fluorescence detectors (HPLC-UV-FLD) and GC coupled to a mass spectrometer (GC-MS) – were compared to separate and quantify oxy-PAHs. Microwave assisted extraction (MAE) was optimized to extract oxy-PAHs from sediments. Results: First OH-PAHs and quinones were analyzed in HPLC with on-line UV and fluorimetric detectors. OH-PAHs were detected with the sensitive FLD, but the non-fluorescent quinones were detected with UV. The limits of detection (LOD)s obtained were in the range (2-3)×10-4 mg/L for OH-PAHs and (2-3)×10-3 mg/L for quinones. Second, even if GC-MS is not well adapted to the analysis of the thermodegradable OH-PAHs and quinones without any derivatization step, it was used because of the advantages of the detector in terms of identification and of GC in terms of efficiency. Without derivatization, only two of the four quinones were detected in the range 1-10 mg/L (LODs=0.3-1.2 mg/L) and LODs were neither very satisfying for the four OH-PAHs (0.18-0.6 mg/L). So two derivatization processes were optimized, comparing to literature: one for silylation of OH-PAHs, one for acetylation of quinones. Silylation using BSTFA/TCMS 99/1 was enhanced using a mixture of catalyst solvents (pyridine/ethyle acetate) and finding the appropriate reaction duration (5-60 minutes). Acetylation was optimized at different steps of the process, including the initial volume of compounds to derivatize, the added amounts of Zn (0.1-0.25 g), the nature of the derivatization product (acetic anhydride, heptafluorobutyric acid…) and the liquid/liquid extraction at the end of the process. After derivatization, LODs were decreased by a factor 3 for OH-PAHs and by a factor 4 for quinones, all the quinones being now detected. Thereafter, quinones and OH-PAHs were extracted from spiked sediments using microwave assisted extraction (MAE) followed by GC-MS analysis. Several mixtures of solvents of different volumes (10-25 mL) and using different extraction temperatures (80-120°C) were tested to obtain the best recovery yields. Satisfactory recoveries could be obtained for quinones (70-96%) and for OH-PAHs (70-104%). Temperature was a critical factor which had to be controlled to avoid oxy-PAHs degradation during the MAE extraction process. Conclusion: Even if MAE-GC-MS was satisfactory to analyze these oxy-PAHs, MAE optimization has to be carried on to obtain a most appropriate extraction solvent mixture, allowing a direct injection in the HPLC-UV-FLD system, which is more sensitive than GC-MS and does not necessitate a previous long derivatization step.

Keywords: derivatizations for GC-MS, microwave assisted extraction, on-line HPLC-UV-FLD, oxygenated PAHs, polluted sediments

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