Unveiling the Aftermath: Exploring Residue Profiles of Insecticides, Herbicides, and Fungicides in Rice Straw, Soils, and Air Post-Mixed Pesticide-Contaminated Biomass Burning.

This study delved into the impact of open biomass burning on the distribution of pesticide and polycyclic aromatic hydrocarbon (PAH) residues across soil, rice straw, total suspended particulates (TSP), particulate matter with aerodynamic diameter ≤ 10 µm (PM10), and aerosols. A combination of herbicides atrazine (ATZ) and diuron (DIU), fungicide carbendazim (CBD), and insecticide chlorpyriphos (CPF) was applied to biomass before burning. Post-burning, the primary soil pesticide shifted from propyzamide (67.6%) to chlorpyriphos (94.8%). Raw straw biomass retained residues from all pesticide groups, with chlorpyriphos notably dominating (79.7%). Ash residue analysis unveiled significant alterations, with elevated concentrations of chlorpyriphos and terbuthylazine, alongside the emergence of atrazine-desethyl and triadimenol. Pre-burning TSP analysis identified 15 pesticides, with linuron as the primary compound (51.8%). Post-burning, all 21 pesticides were detected, showing significant increases in metobromuron, atrazine-desethyl, and cyanazine concentrations. PM10 composition mirrored TSP but exhibited additional compounds and heightened concentrations, particularly for atrazine, linuron, and cyanazine. Aerosol analysis post-burning indicated a substantial 39.2-fold increase in atrazine concentration, accompanied by the presence of sebuthylazine, formothion, and propyzamide. Carcinogenic PAHs exhibited noteworthy post-burning increases, contributing around 90.1 and 86.9% of all detected PAHs in TSP and PM10, respectively. These insights advance understanding of pesticide dynamics in burning processes, crucial for implementing sustainable agricultural practices and safeguarding environmental and human health.

Airborne Pesticides-Deep Diving into Sampling and Analysis.

The escalating utilization of pesticides has led to pronounced environmental contamination, posing a significant threat to agroecosystems. The extensive and persistent global application of these chemicals has been linked to a spectrum of acute and chronic human health concerns. This review paper focuses on the concentrations of airborne pesticides in both indoor and outdoor environments. The collection of diverse pesticide compounds from the atmosphere is examined, with a particular emphasis on active and passive air sampling techniques. Furthermore, a critical evaluation is conducted on the methodologies employed for the extraction and subsequent quantification of airborne pesticides. This analysis takes into consideration the complexities involved in ensuring accurate measurements, highlighting the advancements and limitations of current practices. By synthesizing these aspects, this review aims to foster a more comprehensive and informed comprehension of the intricate dynamics related to the presence and measurement of airborne pesticides. This, in turn, is poised to significantly contribute to the refinement of environmental monitoring strategies and the augmentation of precise risk assessments.

Airborne Pesticides from Agricultural Practices: A Critical Review of Pathways, Influencing Factors, and Human Health Implications.

This critical review examines the release of pesticides from agricultural practices into the air, with a focus on volatilization, and the factors influencing their dispersion. The review delves into the effects of airborne pesticides on human health and their contribution to anthropogenic air pollution. It highlights the necessity of interdisciplinary research encompassing science, technology, public policy, and agricultural practices to effectively mitigate the risks associated with pesticide volatilization and spray dispersion. The text acknowledges the need for more research to understand the fate and transport of airborne pesticides, develop innovative application technologies, improve predictive modeling and risk assessment, and adopt sustainable pest management strategies. Robust policies and regulations, supported by education, training, research, and development, are crucial to ensuring the safe and sustainable use of pesticides for human health and the environment. By providing valuable insights, this review aids researchers and practitioners in devising effective and sustainable solutions for safeguarding human health and the environment from the hazards of airborne pesticides.

Biodegradation Capabilities of Paraquat-Degrading Bacteria Immobilized on Nanoceramics.

The biodegradation of paraquat was investigated using immobilized microbial cells on nanoceramics fabricated from nanoscale kaolinite. Pseudomonas putida and Bacillus subtilis, which degrade paraquat, were immobilized separately on nanoceramics (respectively called ICnc-P and ICnc-B). The attachment of bacteria to nanoceramics resulted from electrostatic force interactions, hydrogen bonding, and covalent bonding (between the cells and the support materials). The initial 10 mg L-1 concentration of paraquat in water was removed by the adsorption process using nanoceramics at 68% and ceramics at 52%, respectively. The immobilized cells on the nanoceramics were able to remove approximately 92% of the paraquat within 10 h, whereas the free cells could only remove 4%. When the paraquat was removed, the cell-immobilized nanoceramics exhibited a significant decrease in dissolved organic nitrogen (DON). ICnc-B was responsible for 34% of DON biodegradation, while ICnc-P was responsible for 22%. Ammonia was identified as the end product of ammonification resulting from paraquat mineralization.

Biochar Derived from Pineapple Leaf Non-Fibrous Materials and Its Adsorption Capability for Pesticides.

Non-fibrous materials (NFMs) are typically discarded during pineapple leaf fiber processing. The underutilized NFM waste was proposed for use in this work as a raw material for the production of biochar . The removal of pesticides (acetamiprid, imidacloprid, or methomyl) from water was then investigated using the NFM derived biochar (NFMBC). The pseudo-second-order kinetic data suggested chemisorption of pesticide on NFMBC. While acetamiprid or imidacloprid adsorption on NFMBC occurred primarily via multi-layered adsorption (best fitted with the Freundlich isotherms), the Sips adsorption isotherms matched with the experimental data, implying heterogeneous adsorption of methomyl on the biochar surface. The adsorption capacities for acetamiprid, methomyl, and imidacloprid are 82.18, 36.16, and 28.98 mg g-1, respectively, which are in agreement with the order of the polarity (low to high) of pesticides. Adsorption capacities indicated that the NFMBC preferably removed low-polarity pesticides from water sources. Since pineapple leaves provide fibers and NFMs for materials development, this study should promote an extended agro-waste utilization approach and full-cycle resource management in pineapple fields.

Photocatalytic removal of 2-chlorophenol from water by using waste eggshell-derived calcium ferrite.

A new approach to recycling low-value eggshell food waste was to produce a CaFe2O4 semiconductor with a narrow band gap (Eg = 2.81 eV) via hydrothermal treatments of powdered eggshell suspended in aqueous ferric salt (Fe3+) solutions at varying Fe loadings. It was possible to obtain a single phase of CaFe2O4 without any Ca(OH)2 and CaO impurities using an optimal Fe loading (30 wt% of Fe3+ by eggshell weight). The CaFe2O4 material was used as a photocatalyst for the breakdown of 2-chlorophenol (2-CP, a herbicide model chemical) as a pollutant in water. The CaFe2O4 with a Fe loading of 7.1 wt% exhibited a high 2-CP removal efficiency of 86.1% after 180 min of UV-visible light irradiation. Additionally, the eggshell-derived CaFe2O4 photocatalyst can be effectively reused, giving a high removal efficiency of 70.5% after the third cycle, without the requirement of regeneration processes (washing or re-calcination). Although radical trapping experiments confirmed that hydroxyl radicals were generated in the photocatalytic reactions, photogenerated holes play a significant role in the high 2-CP degradation efficiencies. The performance of the bioderived CaFe2O4 photocatalysts in the removal of pesticides from water demonstrated the benefits of resource recycling in the area of materials science and in environmental remediation and protection.

Photocatalytic Activity of TiO2/g-C3N4 Nanocomposites for Removal of Monochlorophenols from Water.

This research employed g-C3N4 nanosheets in the hydrothermal synthesis of TiO2/g-C3N4 hybrid photocatalysts. The TiO2/g-C3N4 heterojunctions, well-dispersed TiO2 nanoparticles on the g-C3N4 nanosheets, are effective photocatalysts for the degradation of monochlorophenols (MCPs: 2-CP, 3-CP, and 4-CP) which are prominent water contaminants. The removal efficiency of 2-CP and 4-CP reached 87% and 64%, respectively, after treatment of 25 ppm CP solutions with the photocatalyst (40TiO2/g-C3N4, 1 g/L) and irradiation with UV-Vis light. Treatment of CP solutions with g-C3N4 nanosheets or TiO2 alone in conjunction with irradiation gave removal efficiencies lower than 50%, which suggests the two act synergically to enhance the photocatalytic activity of the 40TiO2/g-C3N4 nanocomposite. Superoxide and hydroxyl radicals are key active species produced during CP photodegradation. In addition, the observed nitrogen and Ti3+ defects and oxygen vacancies in the TiO2/g-C3N4 nanocomposites may improve the light-harvesting ability of the composite and assist preventing rapid electron-hole recombination on the surface, enhancing the photocatalytic performance. In addition, interfacial interactions between the MCPs (low polarity) and thermally exfoliated carbon nitride in the TiO2/g-C3N4 nanocomposites may also enhance MCP degradation.

Challenges and effectiveness of nanotechnology-based photocatalysis for pesticides-contaminated water: A review.

Pesticides have been frequently used in agricultural fields. Due to the expeditious utilization of pesticides, their excessive usage has negative impacts on the natural environment and human health. This review discusses the successful implications of nanotechnology-based photocatalysis for the removal of environmental pesticide contaminants. Notably, various nanomaterials, including TiO2, ZnO, Fe2O3, nanoscale zero-valent iron, nanocomposite-based materials, have been proposed and have played a progressively essential role in wastewater treatment. In addition, a detailed review of the crucial reaction condition factors, including water matrix, pH, light source, temperature, flow rate (retention time), initial concentration of pesticides, a dosage of photocatalyst, and radical scavengers, is also highlighted. Additionally, the degradation pathway of pesticide mineralization is also elucidated. Finally, the challenges of technologies and the future of nanotechnology-based photocatalysis toward the photo-degradation of pesticides are thoroughly discussed. It is expected that those innovative extraordinary photocatalysts will significantly enhance the performance of pesticides degradation in the coming years.

Using ZrO2 coated sludge from drinking water treatment plant as a novel adsorbent for nitrate removal from contaminated water.

This study aimed to produce a novel efficient absorbent using sludge generated from drinking water treatment plants (DWTPs) as a low-cost absorbent and applied to treat nitrate (NO3-) from contaminated water. Before the ZrO2 coating experiment, the drinking water sludge (DWS) from DWTPs was pretreated by thermal treatment (80 °C, 200 °C, and 500 °C). After that, ZrO2 coated drinking water sludge (DWS@ZrO2) was produced by a simple precipitated reaction. The synthesized DWS@ZrO2 was characterized by FTIR, SEM, and EDS with mapping analysis, XRD, and VSM. The results revealed that DWS@ZrO2 could improve the pore filling in the adsorption experiment. The highest nitrate adsorption capacity was achieved (30.99 mg g- 1) at pH 2 with DWS500@ZrO2. Adsorption kinetics indicated that pyrolyzed DWS at 500 °C provided the highest nitrate adsorption capacity, followed by 200 °C, and 80 °C. Thermodynamic results showed that the obtained nitrate removal was an endothermic and spontaneous process. The possible nitrate adsorption mechanism of DWS@ZrO2 could mainly involve pore filling, electrostatic interaction, and ligand exchange. The experimental results suggest that DWS@ZrO2 is a feasible absorbent with high-efficiency, low-cost, high recyclability, and eco-friendly characteristics for treating nitrate in an aqueous solution.

Unintentional release of antibiotics associated with nutrients recovery from source-separated human urine by biochar.

The use of biochar to recover nitrogen and phosphorus from wastewater especially source-separated human urine is attractive from both economic and environmental standpoints. The widespread use of pharmaceuticals has raised concerns as they are not fully metabolized and ended up in human urine. The objective of this study is to examine adsorption of antibiotics (azithromycin, ciprofloxacin, sulfamethoxazole, trimethoprim, and tetracycline) and nutrients (ammonium and phosphate) in source-separated human urine by biochar and subsequent desorption. Batch adsorption experiments were conducted using biochar prepared from oak wood (OW) and paper mill sludge (PMS) to elucidate the effects of adsorption time, pH, and adsorbent dose. The desorption of adsorbed nutrients and antibiotics was also investigated. While the nutrient adsorption was more favorable by the PMS biochar, antibiotic adsorption was more prolific by the OW biochar. Hydrogen bonding and π-π interaction were identified as potential adsorption mechanisms. Experimental results agree with the Freundlich isotherm and pseudo-second order models (except the OW biochar for the kinetics). The findings suggest that biochar can adsorb both nutrients (43.30-266.67 mg g-1) and antibiotics (246.70-389.0 µg g-1) simultaneously. Lower solution pH (<5) was better for antibiotic adsorption, while higher solution pH (≥5) favored nutrient recovery. Also, desorption of the antibiotics (maximum of 92.6% for trimethoprim) was observed and might arise in the environment with the applications of biochar for nutrient recovery from human urine and subsequently for soil quality improvement. The findings serve as a foundation for future research on adsorption-based methods for separating nutrients and antibiotics in aqueous solutions, particularly urine.

Pesticide use in Thailand: Current situation, health risks, and gaps in research and policy.

Agriculture in Thailand, which employs over 30 percent of the workforce and contributes significantly to the country's gross domestic product, is a key sector of its economy. Import and use of pesticides has increased over the past decade due to Thailand's major role as a leading exporter of food and agricultural products. The widespread and poorly regulated use of pesticides presents a potential risk to the health of farmers, farm families, the general population including children and the environment. This article is a result of the Southeast Asia GEOHealth Network Meeting of February 2019. It summarizes the current situation on pesticide use and regulation in Thailand and reports research findings on the potential health and environmental impacts of pesticide use, as well as highlighting gaps in research that could play an important and influential role in future policy initiatives on pesticides. Although Thailand has made remarkable progress in improving agricultural health and safety and similarly strong research and policy programs are being developed in other countries in the region, there are still significant gaps in research and policy that need to be filled.

Biodegradation of paraquat by Pseudomonas putida and Bacillus subtilis immobilized on ceramic with supplemented wastewater sludge.

This work aimed to study the performance of paraquat removal by cell-immobilized ceramics. Two strains of paraquat degrading bacteria, Pseudomonas putida and Bacillus subtilis, were separately immobilized on the ceramic with and without wastewater sludge addition. Results showed that the ceramic surface with sludge has more functional groups and a more highly negative charge on the surface than the original ceramic. The ceramic with sludge had 2-3-fold of the immobilized cells higher than that of the control (without sludge) and less leaching of the immobilized cells. The sludge addition at 20% (w/w) to the ceramic provided the highest cell adhesion for both P. putida and B. subtilis. The paraquat removal efficiencies were higher than 98%, while the control ceramic could remove only 77 ± 1.2%. The immobilized cells on ceramic with sludge provided a significant degree of dissolved organic nitrogen reduction (82%) during the paraquat removal. Most organic nitrogen in paraquat was biologically mineralized (ammonified). Findings from this work suggest the superiority of ceramic with sludge in mineralizing organic nitrogen associated with paraquat.

Tailored photocatalysts and revealed reaction pathways for photodegradation of polycyclic aromatic hydrocarbons (PAHs) in water, soil and other sources.

Polycyclic aromatic hydrocarbons (PAHs), which are in the class of persistent organic pollutants, are considered as hazardous pollutants. To date, these compounds were detected globally in soil, sludge, water, and other contamination sources. A variety of treatment methods have been used in recent years to degrade PAHs in the environment. Photocatalysis, among advanced techniques, is proposed as the most effective method for the treatment of PAHs. In this context, we introduce the classification of PAHs, summarize, and highlight the recent studies on photodegradation of various types of PAHs. A series of efficient photocatalysts, including TiO2-, Ag3PO4-, ZnO-, MHCFs-based, and others, have been reported with the potential result for photodegradation of PAHs. Focus is also placed on revealing several possible reaction pathways for different types of PAHs that have been proposed in the literature. Particular attention to current status, challenges, and prospects in the future for enhanced photodegradation of PAHs are also discussed.

Similarities and differences in adsorption mechanism of dichlorvos and pymetrozine insecticides with coconut fiber biowaste sorbent.

In this study, the similarities and differences of the adsorption mechanisms between dichlorvos and pymetrozine and coconut fiber biowaste sorbent (CF-BWS) were investigated. CF-BWS was produced using the slow pyrolysis process at 600 °C for 4 h. HCl acid modification was used to improve the specific surface area. The properties of CF-BWS were analyzed by SEM, FT-IR, BET, and pHpzc. The adsorption kinetics of dichlorvos and pymetrozine on the CF-BWS were well explained by the pseudo-second-order model. The adsorption isotherms for both insecticides were followed the Langmuir isotherm. The difference in molecular structures and surface chemistry caused the difference in adsorption mechanisms of both insecticides. The pore-filling and the hydrophobic interactions were the key mechanisms for both insecticide adsorptions. However, the π-π electron donor-acceptor interaction played the major role in the pymetrozine adsorption but hardly impacted on the adsorption of dichlorvos. The hydrogen bonding mechanism was pronounced in the pymetrozine adsorption, but it had little influence on the dichlorvos adsorption. The CF-BWS is exhibited as an excellent material for the removal of both pollutants and has high potential to be used further as the adsorbent in water treatment process.

Adsorption mechanism of dichlorvos onto coconut fibre biochar: the significant dependence of H-bonding and the pore-filling mechanism.

The adsorption mechanism of dichlorvos onto coconut fibre biochar (CFB) was investigated by the batch adsorption technique. Coconut fibre waste material was synthesised at 600 °C for 4 h under oxygen-limited conditions. The biochar was modified by HCl acid to enhance the specific surface area and porosity. The characteristics of the biochar were analysed by scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) specific surface area, and Fourier transform-infrared (FT-IR). The results showed that the BET specific surface area of biochar was 402.4 m2/g. Experimental data presented a good fit to Langmuir isotherm and the pseudo-second-order model. Langmuir isotherm illustrated that monolayer adsorption of dichlorvos occurred on the surface of CFB, with a maximum adsorption capacity of 90.9 mg/g. The diffusion model confirmed that the liquid film diffusion was the rate-limiting step, and the major diffusion mechanism of dichlorvos onto biochar. The BET result after dichlorvos adsorption demonstrated that pore-filling occurred and occupied 58.27%. The pore-filling and chemical interactions, performed important roles in the adsorption of dichlorvos onto CFB. Chemical adsorption is comprised of two interactions, which are hydrophobic and H-bonding, but the prime is H-bonding. CFB is a very potential material for the removal of dichlorvos and environmental pollutants.

Degradation of paraquat from contaminated water using green TiO2 nanoparticles synthesized from Coffea arabica L. in photocatalytic process.

The TiO2 nanoparticles synthesized from the extract of Coffea arabica L. (or TiO2/C) were used to remove paraquat from contaminated water in heterogeneous photocatalysis process. In this work, the sol-gel process using Coffea arabica L. as the solvent chemical were performed to obtain the TiO2 nano-catalyst. The value of pHpzc of TiO2/C was 2.9 which caused a highly acidic surface of catalyst. The paraquat is effectively removed in alkaline medium due to the adsorption ability of paraquat on the surface of TiO2/C. The paraquat degradation followed the pseudo-first-order model with the apparent rate constants of 5.84 × 10-2, 4.08 × 10-2, and 2.28 × 10-2 min-1 for TiO2/C, TiO2, and without TiO2, respectively, under the presence of ultraviolet (UV) and H2O2. The combined TiO2/C with UV and H2O2 was the most efficient process, exhibiting a maximum 66.3% degradation of 50 mg/L over 90 min at pH 10.

Coupling HYDRUS-1D with ArcGIS to estimate pesticide accumulation and leaching risk on a regional basis.

HYDRUS-1D is a well-established reliable instrument to simulate water and pesticide transport in soils. It is, however, a point-specific model which is usually used for site-specific simulations. Aim of the investigation was the development of pesticide accumulation and leaching risk maps for regions combining HYDRUS-1D as a model for pesticide fate with regional data in a geographical information system (GIS). It was realized in form of a python tool in ArcGIS. Necessary high resolution local soil information, however, is very often not available. Therefore, worldwide interpolated 250-m-grid soil data (SoilGrids.org) were successfully incorporated to the system. The functionality of the system is shown by examples from Thailand, where example regions that differ in soil properties and climatic conditions were exposed in the model system to pesticides with different properties. A practical application of the system will be the identification of areas where measures to optimize pesticide use should be implemented with priority.

Formation of hydroxyl radicals and kinetic study of 2-chlorophenol photocatalytic oxidation using C-doped TiO2, N-doped TiO2, and C,N Co-doped TiO2 under visible light.

This work reports on synthesis, characterization, adsorption ability, formation rate of hydroxyl radicals (OH(•)), photocatalytic oxidation kinetics, and mineralization ability of C-doped titanium dioxide (TiO2), N-doped TiO2, and C,N co-doped TiO2 prepared by the sol-gel method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy were used to analyze the titania. The rate of formation of OH(•) for each type of titania was determined, and the OH-index was calculated. The kinetics of as-synthesized TiO2 catalysts in photocatalytic oxidation of 2-chlorophenol (2-CP) under visible light irradiation were evaluated. Results revealed that nitrogen was incorporated into the lattice of titania with the structure of O-Ti-N linkages in N-doped TiO2 and C,N co-doped TiO2. Carbon was joined to the Ti-O-C bond in the C-doped TiO2 and C,N co-doped TiO2. The 2-CP adsorption ability of C,N co-doped TiO2 and C-doped TiO2 originated from a layer composed of a complex carbonaceous mixture at the surface of TiO2. C,N co-doped TiO2 had highest formation rate of OH(•) and photocatalytic activity due to a synergistic effect of carbon and nitrogen co-doping. The order of photocatalytic activity per unit surface area was the same as that of the formation rate of OH(•) unit surface area in the following order: C,N co-doped TiO2 > C-doped TiO2 > N-doped TiO2 > undoped TiO2.

Visible light photocatalytic antibacterial activity of Ni-doped and N-doped TiO2 on Staphylococcus aureus and Escherichia coli bacteria.

The Ni-doped and N-doped TiO2 nanoparticles were investigated for their antibacterial activities on Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) bacteria. Their morphological features and characteristics such as particle size, surface area, and visible light absorbing capacity were compared and discussed. Scanning electron microscopy, X-ray diffraction, and UV-visible spectrophotometry were used to characterize both materials. The inactivation of E. coli (as an example of Gram-negative bacteria) and S. aureus (as an example of Gram-positive bacteria) with Ni-doped and N-doped TiO2 was investigated in the absence and presence of visible light. Antibacterial activity tests were conducted using undoped, Ni-doped, and N-doped TiO2. The N-doped TiO2 nanoparticles show higher antibacterial activity than Ni-doped TiO2. The band gap narrowing of N-doped TiO2 can induce more visible light absorption and leads to the superb antibacterial properties of this material. The complete inactivation time for E. coli at an initial cell concentration of 2.7 × 10(4) CFU/mL was 420 min which is longer than the 360 min required for S. aureus inactivation. The rate of inactivation of S. aureus using the doped TiO2 nanoparticles in the presence of visible light is greater than that of E. coli. The median lethal dose (LD50) values of S. aureus and E. coli by antibacterial activity under an 18-W visible light intensity were 80 and 350 mg/ml for N-doped TiO2, respectively.