Validation of QuEChERS method for the determination of some pesticide residues in two apple varieties

This study was undertaken to validate the “quick, easy, cheap, effective, rugged and safe” (QuEChERS) method using Golden Delicious and Starking Delicious apple matrices spiked at 0.1 maximum residue limit (MRL), 1.0 MRL and 10 MRL levels of the four pesticides (chlorpyrifos, dimethoate, indoxacarb and imidacloprid). For the extraction and cleanup, original QuEChERS method was followed, then the samples were subjected to liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) for chromatographic analyses. According to t test, matrix effect was not significant for chlorpyrifos in both sample matrices, but it was significant for dimethoate, indoxacarb and imidacloprid in both sample matrices. Thus, matrix-matched calibration (MC) was used to compensate matrix effect and quantifications were carried out by using MC. The overall recovery of the method was 90.15% with a relative standard deviation of 13.27% (n = 330). Estimated method detection limit of analytes blew the MRLs. Some other parameters of the method validation, such as recovery, precision, accuracy and linearity were found to be within the required ranges.     

Preliminary investigation of sensitive biomarkers of trace metal pollution in mussel (Mytilus galloprovincialis) from Izmir Bay (Turkey)

The aim of this study was to identify possible relationships between biochemical- superoxide dismutase (SOD), glutathione peroxidase (GPx), thiobarbituric acid reactive substances (TBARS) of mussels (Mytilus galloprovincialis) and chemical (Hg, Cd, Pb, Cr, Cu, Zn, Mn and Fe) contaminants from relatively clean area (Middle Bay) and heavily polluted area (Inner Bay) of the Izmir Bay. Sampling of mussels was performed in the beginning of May 2004. Mussel digestive glands have been used for biochemical assays. Trace metal content was determined by atomic absorption spectrophotometer using standard procedures. Metal contents in mussels collected at polluted site increased compared to the middle part of the bay. While there was a positive correlation between metals and SOD enzyme activity, there was a negative correlation between metals and GPx enzyme activity. An increase was observed in SOD enzyme activity and a decrease of GPx enzyme activity at the inner part of the bay.     

Biotope mapping in an urban environment and its implications for urban management in Turkey

The biotopes of ecological importance in urban environments worldwide are under the pressure of many negative factors such as urbanization, air pollution, human disturbance, etc. Biotope mapping is an important tool for urban planning and management and of importance for the protection of biotopes for future generations. The biotopes in Antalya city of Turkey, which has faced to a great population pressure due to tourism developments and immigration in the last two decades, were investigated in this study. The selective biotope mapping method was used and major biotope sites were determined by the interpretation of panchromatic aerial photographs, assisted with field verifications. A sensitivity assessment based on two parameters, the rarity and the re-establishment ability of biotopes, was made as it was considered important information for urban planning and management. According to the results of the assessment, the majority of biotopes in Antalya city were found to be very sensitive or sensitive. It was concluded that insufficient legislation, the lack of an ecological urban planning approach and poor urban management are the most important reasons for today's pressures on urban biotopes in Turkey.     

Effects of chitosan on oxidative stress and metallothioneins in aquatic worm Tubifex tubifex (Oligochaeta, Tubificidae)

Chitosan is a natural polymer which has the property to elicit the natural defenses mechanism in plant and which can be an interesting biopesticides. It is then necessary to investigate the potential toxicity of chitosan for aquatic animal health. Metallothioneins (MTs) are low molecular weight proteins, mainly implicated in metal ion detoxification. Increase in MTs contents had been considered as a specific biomarker of metal exposure. However recently it has been demonstrated that MTs participate in several cellular functions such as regulation of growth and anti-oxidative defenses. Therefore, the induction of MTs has been investigated in the aquatic worms Tubifex tubifex exposed to chitosan. MTs levels in exposed worm increased significantly (p > 0.05) after 2, 4, and 7 days of exposure to different concentrations of chitosan (maximum + 158.19 +/- 10.2% after 2 days of exposure to 125 mgl(-1) of chitosan). Several antioxidant parameters including glutathione (GSH), glutathione-S-transferase (GST), glutathione reductase (GR), and catalase (CAT) were quantified in T. tubifex after 2, 4, and 7 days of exposure to chitosan. Exposure to chitosan had a negative effect on T. tubifex growth (maximum effect -6.11 +/- 1.6% after 7 days with 125 mgl(-1)) demonstrating the toxic effect of the pesticide. This growth rate decrease was accompanied by a reduction in protein contents. The activity of catalase (CAT), glutathione-S-transferase (GST), and glutathione reductase (GR) increased in response to the chitosan demonstrating an oxidative stress in the worms.     

Machine learning and computational chemistry to improve biochar fertilizers: a review

Traditional fertilizers are highly inefficient, with a major loss of nutrients and associated pollution. Alternatively, biochar loaded with phosphorous is a sustainable fertilizer that improves soil structure, stores carbon in soils, and provides plant nutrients in the long run, yet most biochars are not optimal because mechanisms ruling biochar properties are poorly known. This issue can be solved by recent developments in machine learning and computational chemistry. Here we review phosphorus-loaded biochar with emphasis on computational chemistry, machine learning, organic acids, drawbacks of classical fertilizers, biochar production, phosphorus loading, and mechanisms of phosphorous release. Modeling techniques allow for deciphering the influence of individual variables on biochar, employing various supervised learning models tailored to different biochar types. Computational chemistry provides knowledge on factors that control phosphorus binding, e.g., the type of phosphorus compound, soil constituents, mineral surfaces, binding motifs, water, solution pH, and redox potential. Phosphorus release from biochar is controlled by coexisting anions, pH, adsorbent dosage, initial phosphorus concentration, and temperature. Pyrolysis temperatures below 600 °C enhance functional group retention, while temperatures below 450 °C increase plant-available phosphorus. Lower pH values promote phosphorus release, while higher pH values hinder it. Physical modifications, such as increasing surface area and pore volume, can maximize the adsorption capacity of phosphorus-loaded biochar. Furthermore, the type of organic acid affects phosphorus release, with low molecular weight organic acids being advantageous for soil utilization. Lastly, biochar-based fertilizers release nutrients 2–4 times slower than conventional fertilizers.

     

Toxicity and biochemical impact of certain oxime carbamate pesticides against terrestrial snail,Theba pisana (Müller)

Abstract

The bran toxic baits (0.5 % w/w) of five oxime carbamate pesticides; aldicarb, aldoxycarb, methomyl, oxamyl and thiofanox were tested for their molluscicidal activity against Theba pisana snails under Laboratory conditions. In addition, the in vivo effects of these compounds on seven vital enzymes namely Acetylcholin‐esterase (AchE), glutathion‐S‐transferase (GST), glutamic oxlaoacetic transaminase (GOT), glutamic pyruvic transaminase (GPT), acid phosphatase (AcP), alkaline phosphatase (AIP), and adenosine triphosphatase (ATPase) activities of the snail tissue were also investigated after 1,3, and 5 days of exposure. The results showed that methomyl was the most potent candidate, whereas thiofanox was the least effective one against the snails. LT₅₀’s values of aldicarb, aldoxycarb, methomyl, oxamyl and thiofanox were 5.77, 4.69, 2.31, 3.97 and 6.67 days, respectively. Results of the potency of the tested pesticides against AchE activity were in harmony with the toxicity of these compounds to snails. AchE, AcP, and AIP activities were inhibited by the tested pesticides. GST activity was inhibited by aldicarb but stimulated by oxamyl and thiofanox. Methomyl and oxamyl lead to significant elevation of GOT and GPT, whereas thiofanox treated snail induced a reduction of both enzymes activities. Aldicarb and aldoxycarb caused significant induction of ATPase activity.     

Pathogen reduction in minimally managed composting of bovine manure

Spread of manure pathogens is of considerable concern due to use of manure for land application. In this study, the effects of four static pile treatment options for bovine manure on die-off of a generic Escherichia coli, E. coli O157:H7 surrogate, Salmonella Senftenberg, Salm. Typhimurium, and Listeria monocytogenes were evaluated. Bovine manure spiked with these bacteria were placed in cassettes at the top, middle, and bottom sections of four static pile treatments that reflect minimal changes in pile construction with and without straw. Temperatures were monitored continuously during the 28 day self-heating period. E. coli and salmonellae were reduced from 8 to 9 log₁₀ CFU g^?1 to undetectable levels (<1.77 log₁₀ MPN g^?1) at 25–30 cm depths within 7 days in all pile sections except for the manure-only pile in which 3–4 logs of reduction were obtained. No L. monocytogenes initially present at 6.62 log₁₀ CFU g^?1 were recovered from straw-amended piles after 14 days, in contrast with manure-only treatment in which this pathogen was recovered even at 28 days. Decline of target bacterial populations corresponded to exposure to temperatures above 45 °C for more than 3 days and amendments of manure with straw to increase thermophilic zones. Use of straw to increase aeration, self-heating capacity, and heat retention in manure piles provides producers a minimal management option for composting that enhances pathogen die-off and thereby reduces risk of environmental spread when manure is applied to land.     

Microplastic sources,formation, toxicity and remediation: a review

Microplastic pollution is becoming a major issue for human health due to the recent discovery of microplastics in most ecosystems. Here, we review the sources, formation, occurrence, toxicity and remediation methods of microplastics. We distinguish ocean-based and land-based sources of microplastics. Microplastics have been found in biological samples such as faeces, sputum, saliva, blood and placenta. Cancer, intestinal, pulmonary, cardiovascular, infectious and inflammatory diseases are induced or mediated by microplastics. Microplastic exposure during pregnancy and maternal period is also discussed. Remediation methods include coagulation, membrane bioreactors, sand filtration, adsorption, photocatalytic degradation, electrocoagulation and magnetic separation. Control strategies comprise reducing plastic usage, behavioural change, and using biodegradable plastics. Global plastic production has risen dramatically over the past 70 years to reach 359 million tonnes. China is the world's top producer, contributing 17.5% to global production, while Turkey generates the most plastic waste in the Mediterranean region, at 144 tonnes per day. Microplastics comprise 75% of marine waste, with land-based sources responsible for 80–90% of pollution, while ocean-based sources account for only 10–20%. Microplastics induce toxic effects on humans and animals, such as cytotoxicity, immune response, oxidative stress, barrier attributes, and genotoxicity, even at minimal dosages of 10 μg/mL. Ingestion of microplastics by marine animals results in alterations in gastrointestinal tract physiology, immune system depression, oxidative stress, cytotoxicity, differential gene expression, and growth inhibition. Furthermore, bioaccumulation of microplastics in the tissues of aquatic organisms can have adverse effects on the aquatic ecosystem, with potential transmission of microplastics to humans and birds. Changing individual behaviours and governmental actions, such as implementing bans, taxes, or pricing on plastic carrier bags, has significantly reduced plastic consumption to 8–85% in various countries worldwide. The microplastic minimisation approach follows an upside-down pyramid, starting with prevention, followed by reducing, reusing, recycling, recovering, and ending with disposal as the least preferable option.

     

Enhanced photocatalytic activity of fish scale loaded TiO2 composites under solar light irradiation

Fish scale (FS) loaded TiO₂ composites were investigated as photocatalysts in degradation of Methyl Orange under solar light irradiation. Composites were prepared through sol-gel method by varying mass ratio of TiO₂/FS at 90:10, 70:30 and 50:50, respectively. The catalysts prepared in this study were characterized by using XRD, SEM, FT-IR and nitrogen sorption. The effects of solar irradiation, mass ratio of TiO₂/FS composites, irradiation time and catalyst loadings were studied. Synergistic effect was found in TiO₂/FS of 90:10 composite which performed higher photocatalytic degradation than synthesized TiO₂ under solar light irradiation. However, further increasing fish scale content in the composites reduced the photocatalytic activity drastically. Under solar light irradiation, all the catalysts in this study exhibited photocatalytic activity, except TiO₂/FS of 50:50 composite that only acted as a weak biosorbent without performing any photocatalytic property. Photocatalytic degradation increased with increasing catalyst loading and irradiation time but decreased with increased of initial dye concentration.