Preparation and characterization of polycaprolactone nanocapsules containing pretilachlor as a herbicide nanocarrier

Polycaprolactone nanocapsules (PCL) containing pretilachlor were prepared, and Fourier transform infrared spectroscopy, atomic force microscopy, and transmission electron microscopy were used for their structural and morphological investigations. The results revealed that the nanocapsules had irregular shape and their particles size was in the range of 70–200 nm. The encapsulation efficiency of pretilachlor was measured as 99.5 ± 1.3% using high-performance liquid chromatography analysis. The physicochemical stability studies over 60 days showed that the nanocapsules were stable in the suspension without any aggregation. The herbicide activity was examined in a pre-emergence manner using barnyard grass as a target plant and rice as a non-target plant. The nanoformulation had no negative effect on rice plant. However, its effect on barnyard grass was significant. The cytotoxicity analysis indicated that the nanocapsulated herbicide is less toxic rather than the commercial formulation. Therefore, encapsulation of pretilachlor in PCL nanocapsules can be used effectively to construct environmentally friendly PCL-herbicide systems in agriculture.

     

Exploitation of subabul stem lignin as a matrix in controlled release agrochemical nanoformulations: a case study with herbicide diuron

The utilization of nanomaterials in the domain of agriculture is at an inception, especially in the development of controlled release agrochemical nanoformulations. The present study demonstrated the potential of subabul stem lignin as a matrix material in agrochemical formulations using nanotechnology. In this study, “nanoprecipitation” method was employed and “optimized” to fabricate a stable herbicide, “diuron nanoformulation” (DNF). “Optimized DNF” (ODNF) has 5.17?±?0.49 % diuron loading efficiency (DLE) and 74.3?±?4 % encapsulation efficiency (EE). The size of nanoparticles in ODNF was 166?±?68 nm as revealed by FESEM/TEM studies. Physicochemical characterization of ODNF by UV, FT-IR, and DSC studies revealed the successful loading of diuron within the lignin matrix. The ODNF exhibited nonlinear biphasic release profile for diuron. Further, the bioefficacy of diuron released from ODNF was tested using canola (Brassica rapa). B. rapa seedlings grown in the soil supplemented with ODNF showed early signs of leaf chlorosis and mortality when compared with seedlings grown in the presence of commercial diuron formulation (CDF) or bulk diuron (BD), respectively. This study not only revealed the exploitation of subabul stem lignin as a “matrix” in the controlled release nanoformulation of diuron but also opened up new avenues for utilizing it as matrix for several other agrochemicals associated with the growth and development of the plant.     

UV–visible light-activated Ag-decorated,monodisperse TiO2 aggregates for treatment of the pharmaceutical oxytetracycline

Noble metal Ag-decorated, monodisperse TiO₂ aggregates were successfully synthesized by an ionic strength-assisted, simple sol–gel method and were used for the photocatalytic degradation of the antibiotic oxytetracycline (OTC) under both UV and visible light (UV–visible light) irradiation. The synthesized samples were characterized by X-ray diffraction analysis (XRD); UV–vis diffuse reflectance spectroscopy; environmental scanning electron microscopy (ESEM); transmission electron microscopy (TEM); high-resolution TEM (HR-TEM); micro-Raman, energy-dispersive X-ray spectroscopy (EDS); and inductively coupled plasma optical emission spectrometry (ICP-OES). The results showed that the uniformity of TiO₂ aggregates was finely tuned by the sol–gel method, and Ag was well decorated on the monodisperse TiO₂ aggregates. The absorption of the samples in the visible light region increased with increasing Ag loading that was proportional to the amount of Ag precursor added in the solution over the tested concentration range. The Brunauer, Emmett, and Teller (The BET) surface area slightly decreased with increasing Ag loading on the TiO₂ aggregates. Ag-decorated TiO₂ samples demonstrated enhanced photocatalytic activity for the degradation of OTC under UV–visible light illumination compared to that of pure TiO₂. The sample containing 1.9 wt% Ag showed the highest photocatalytic activity for the degradation of OTC under both UV–visible light and visible light illumination. During the experiments, the detected Ag leaching for the best TiO₂-Ag photocatalyst was much lower than the National Secondary Drinking Water Regulation for Ag limit (0.1 mg L^?1) issued by the US Environmental Protection Agency.     

高锰酸钾缓释剂的制备及其性能研究

利用油相相分离法微胶囊技术,以硬脂酸为壳物质,制备高锰酸钾缓释剂,通过条件优化实验,确定最佳工艺条件为:壳核比值为3∶1、搅拌速度450 r/min以及超声时间为10 min。所制的高锰酸钾缓释剂包覆率为163.3%,在水中缓释行为符合Q=0.00518×t0.611(R2=0.9951)动力学方程,理论缓释期为229.4 d,具有较好的缓释效果。对高锰酸钾缓释剂进行红外光谱和环境电镜扫描分析,结果表明,成膜前后硬脂酸的结构发生改变,硬脂酸对高锰酸钾的微胶囊化不是简单的物理吸附,而是通过化学键合包覆在高锰酸钾表面。     

2,4-dichlorophenoxyacetic acid (2,4-D) micropollutant herbicide removing from water using granular and powdered activated carbons: a comparison applied for water treatment and health safety

Abstract

Activated carbons are well-known porous materials as an effective adsorbent used for the removal of emerging contaminants, such as herbicides, which are increasingly present in water bodies. Most water treatment plants, specially in Brazil, are unable to completely remove such contaminants by the conventional process and advanced treatment using activated carbons is required. The aim of this paper was to verify the influence of the activated carbons granulometry and specific surface area on the 2,4-dichlorophenoxyacetic acid (2,4-D) herbicide removal efficiency using distilled-deionized water and filtered water collected from a conventional Water Treatment Plant. Commercial activated carbons samples used in this work were obtained from two different manufacturers. Activated carbons were analyzed by the specific surface area, pore size and volume distribution, nuclear magnetic resonance, infrared and x-ray spectroscopy, moisture, volatile matter and ash contents. Batch adsorption isotherms experiments were used and performed by Langmuir and Freundlich models. Granular and powdered activated carbons removed over 99% of 2,4-D in distilled water and near to 99% using filtered water. The activated carbons evaluated in this work presented high performance and played a key role in water treatment by removing 2,4-D herbicide, ensuring the protection of human health and the ecosystem.     

Bio-absorption of Ni and Cd on Eichhornia crassipes root thin film

Release of heavy metals into waterways without treatment can cause a significant threat to the environment. In this paper, we present a method of improving the removal of heavy metals by using Eichhornia crassipes roots (ECR) supported on a polymethyl methacrylate (PMMA) thin film. The functional groups of the synthesized PMMA sample were identified by Fourier transform infrared spectroscopy. ECR roots dried fine powder has a small size and large surface area. They contain many polyfunctional metal-binding sites for both cationic and anionic metal complexes. The results show that using 0.1 g of ECR, about 70 % of Cd present in the water was removed in 4 h; while under the same conditions, about 55 % of Ni was removed. The concentrations of Ni and Cd were measured by laser-induced breakdown spectroscopy, a promising technique for the elemental analysis of heavy metals.     

以废纸为原料制备煤尘抑制剂的合成及应用

采用碱化、醚化法制备了以废纸为原料的煤尘抑制剂,借助FTIR、SEM、TG-DTA及XRF等手段对合成物进行了表征,并将其用于抑制煤尘进行性能测试。结果表明,羧甲基纤维素的取代度为0.69;选用羧甲基纤维素含量为0.5g/mL的煤尘抑制剂进行应用实验,效果最佳。9 h内,喷洒含有羧甲基纤维素的煤尘抑制剂的煤样表面已经结壳,抗七级风,抑尘率在130 h都可保持在99%以上。在较高温燃烧条件下,煤尘抑制剂以H2O和CO2的形式失去,不会产生有害物质。     

Analysis of VOCs in Ambient Air Using Multisorbent Packings for VOC Accumulation and Sample Drying

Abstract

Solid multisorbent packings have been characterized for trapping and release efficiency of trace (10-20 ppbv in humidified zero air) volatile organic compounds (VOCs). The use of a two-stage trapping system reduces sample water content typically by more than 95.5% while maintaining a trapping and release efficiency of 100% for 49 VOCs, including eight water-soluble VOCs. Three combinations of primary tube and focusing tube are examined in detail by using an atomic emission detector to monitor hydrogen as an indication of residual water vapor, and to monitor either chlorine, bromine, or carbon for target VOCs. Linearity of response to individual VOCs, the presence of artifacts, and a laboratory monitoring application are also discussed.     

Iron improving bio-char derived from microalgae on removal of tetracycline from aqueous system

Novel magnetic carbonaceous bio-char was hydrothermal prepared from microalgae under different loadings of iron and its structures and surface chemistry were characterized with Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and nitrogen adsorption-desorption isotherm (BET). The morphology of bio-char changed from sheet to particle as iron loading increased and its surface area also increased. When 3.0 g of dried microalgae and 6.0 mmol iron salt ((NH₄)₂SO₄·FeSO₄·6H₂O) were mixed and treated, the obtained bio-char possessing the highest amount of oxygen-containing functional groups resulted in the best adsorption performance on tetracycline (TC). This adsorption process was fitted to Langmuir adsorption isotherm and the maximum adsorption capacity was 95.86 mg/g, which is higher than other bio-char reported. The iron loading contributed to the higher adsorption capacity of bio-char, which may be due to three factors, the high surface area, more hydrogen bonding, and bridging effects of the structural Fe for TC. Our data suggest that bio-char may have more important role in stabilization of pollutants in the environment.     

Development of controlled release formulations of imidacloprid employing novel nano-ranged amphiphilic polymers

Amphiphilic copolymers, synthesized from poly (ethylene glycols) and various aliphatic diacids, which self assemble into nano-micellar aggregates in aqueous media, were used to develop controlled release (CR) formulations of imidacloprid [1-(6 chloro-3-pyridinyl methyl)-N- nitro imidazolidin-2- ylideneamine] using encapsulation technique. High solubilisation power and low critical micelle concentration (CMC) of these amphiphilic polymers may increase the efficacy of formulations. Formulations were characterised by Infrared (IR) spectroscopy, Dynamic Light Scattering (DLS) and Transmission Electron Microscope (TEM). Encapsulation efficiency, loading capacity and stability after accelerated storage test of the developed formulations were checked. The kinetics of imidacloprid release in water from the different formulations was studied. Release from the commercial formulation was faster than the CR formulations. The diffusion exponent (n value) of imidacloprid, in water ranged from 0.22 to 0.37 in the tested formulations. While the time taken for release of 50 % of imidacloprid ranged from 2.32 to 9.31 days for the CR formulations. The developed CR formulations can be used for efficient pest management in different crops.     

Development of controlled release formulations of imidacloprid employing novel nano-ranged amphiphilic polymers

Amphiphilic copolymers, synthesized from poly (ethylene glycols) and various aliphatic diacids, which self assemble into nano-micellar aggregates in aqueous media, were used to develop controlled release (CR) formulations of imidacloprid [1-(6 chloro-3-pyridinyl methyl)-N-nitro imidazolidin-2-ylideneamine] using encapsulation technique. High solubilisation power and low critical micelle concentration (CMC) of these amphiphilic polymers may increase the efficacy of formulations. Formulations were characterised by Infrared (IR) spectroscopy, Dynamic Light Scattering (DLS) and Transmission Electron Microscope (TEM). Encapsulation efficiency, loading capacity and stability after accelerated storage test of the developed formulations were checked. The kinetics of imidacloprid release in water from the different formulations was studied. Release from the commercial formulation was faster than the CR formulations. The diffusion exponent (n value) of imidacloprid, in water ranged from 0.22 to 0.37 in the tested formulations. While the time taken for release of 50 % of imidacloprid ranged from 2.32 to 9.31 days for the CR formulations. The developed CR formulations can be used for efficient pest management in different crops.     

Mustard plant ash: a source of micronutrient and an adsorbent for removal of 2,4-dichlorophenoxyacetic acid

The work highlights the utilization of an agricultural waste mustard plant ash (MPA) as a soil additive and an adsorbent. MPA was characterized by X-ray fluorescence (XRF), energy-dispersive X-ray spectroscopy (EDX), proximate analysis, CHNS analysis, Brunauer–Emmett–Teller (BET) surface area analysis, zeta potential measurements, Fourier transform infrared (FTIR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). XRF analysis confirmed the presence of CaO (31.35 %), K₂O (18.55 %), and P₂O₅ (6.99 %), all of which act as micronutrients to plants. EDX also confirms high amount of elemental O, Ca, K, and P. The adsorptive ability of MPA was investigated using a commonly used herbicide, 2,4-dichlorophenoxyacetic acid (2,4-D), as a representative chemical. Batch adsorption experiments were conducted to study the effect of different operational parameters such as adsorbent dose, initial 2,4-D concentration, contact time, and temperature on the adsorption process. Data from experiments were fitted to various kinetic and isothermal models. The pseudo-second-order kinetic model was found to show the best fit (R ²?>?0.99), with the highest k ₂ value of the order 10⁵. Based on the study results, dosage of MPA/hectare for different crops has been recommended for effective removal of 2,4-D. To our knowledge, this is the first study in which MPA has been characterized in detail and investigated for dual applications (as an adsorbent and as a soil additive).     

Modifying sorbents in controlled release formulations to prevent herbicides pollution

The herbicides chloridazon and metribuzin, identified as groundwater pollutants, were incorporated in alginate-based granules to obtain controlled release properties. In this research the effect of incorporation of sorbents such as bentonite, anthracite and activated carbon in alginate basic formulation were not only studied on encapsulation efficiency but also on the release rate of herbicides which was studied using water release kinetic tests. In addition, sorption studies of herbicides with bentonite, anthracite and activated carbon were made. The kinetic experiments of chloridazon and metribuzin release in water have shown that the release rate is higher in metribuzin systems than in those prepared with chloridazon, which has lower water solubility. Besides, it can be deduced that the use of sorbents reduces the release rate of the chloridazon and metribuzin in comparison to the technical product and to the alginate formulation without sorbents. The highest decrease in release rate corresponds to the formulations prepared with activated carbon as a sorbent. The water uptake, permeability, and time taken for 50% of the active ingredient to be released into water, T(50), were calculated to compare the formulations. On the basis of a parameter of an empirical equation used to fit the herbicide release data, the release of chloridazon and metribuzin from the various formulations into water is controlled by a diffusion mechanism. Sorption capacity of the sorbents for chloridazon and metribuzin, ranging from 0.53mgkg(-1) for the metribuzin sorption on bentonite to 2.03x10(5)mgkg(-1) for the sorption of chloridazon on the activated carbon, was the most important factor modulating the herbicide release.     

Synthetic TiO2 nanoparticle emission from exterior facades into the aquatic environment

We present direct evidence of the release of synthetic nanoparticles from urban applications into the aquatic environment. We investigated TiO₂ particles as these particles are used in large quantities in exterior paints as whitening pigments and are to some extent also present in the nano-size range.TiO₂ particles were traced from exterior facade paints to the discharge into surface waters. We used a centrifugation based sample preparation which recovers TiO₂ particles between roughly 20 and 300 nm. Analytical electron microscopy revealed that TiO₂ particles are detached from new and aged facade paints by natural weather conditions and are then transported by facade runoff and are discharged into natural, receiving waters. Microscopic investigations are confirmed by bulk chemical analysis. By combining results from microscopic investigations with bulk chemical analysis we calculated the number densities of synthetic TiO₂ particles in the runoff.     

Molecular study of concentrated copper pollutant with a compost

Humic substance in compost contains various organic functional groups that can sorb metal ions through ionic force. This study used thermal treatment technology to concentrate copper in the heated residues while destroying the humic substance of copper-sorbed kitchen compost. Scanning electron microscopy (SEM) results show that copper clusters were formed in the heated residues. Information from both X-ray diffraction (XRD) patterns and Cu K-edge X-ray absorption spectroscopy (XAS) spectrum indicates that about 30% of the doped Cu(II) was chemically reduced to Cu(I) and Cu(0) when the sample was heated at 500 and 900 degrees C for 2h. The XAS results indicate that after 500 degrees C thermal treatment, the loaded Cu(NO(3))(2) was transformed into CuO (ca. 54%), Cu (ca. 18%), Cu(OH)(2) (ca. 15%), and Cu(2)O (ca.13%). Heating at 900 degrees C caused more transformation into elemental Cu probably due to more release of oxygen.     

Effects of water-emulsified fuel on a diesel engine generator’s thermal efficiency and exhaust

Water-emulsified diesel has proven itself as a technically sufficient improvement fuel to improve diesel engine fuel combustion emissions and engine performance. However, it has seldom been used in light-duty diesel engines. Therefore, this paper focuses on an investigation into the thermal efficiency and pollution emission analysis of a light-duty diesel engine generator fueled with different water content emulsified diesel fuels (WD, including WD-0, WD-5, WD-10, and WD-15). In this study, nitric oxide, carbon monoxide, hydrocarbons, and carbon dioxide were analyzed by a vehicle emission gas analyzer, and the particle size and number concentration were measured by an electrical low-pressure impactor. In addition, engine loading and fuel consumption were also measured to calculate the thermal efficiency. Measurement results suggested that water-emulsified diesel was useful to improve the thermal efficiency and the exhaust emission of a diesel engine. Obviously, the thermal efficiency was increased about 1.2 to 19.9%. In addition, water-emulsified diesel leads to a significant reduction of nitric oxide emission (less by about 18.3 to 45.4%). However, the particle number concentration emission might be increased if the loading of the generator becomes lower than or equal to 1800 W. In addition, exhaust particle size distributions were shifted toward larger particles at high loading. The consequence of this research proposed that the water-emulsified diesel was useful to improve the engine performance and some of exhaust emissions, especially the NO emission reduction.

Implications:The accumulated test results provide a good basis to resolve the corresponding pollutants emitted from a light-duty diesel engine generator. By measuring and analyzing transforms of exhaust pollutant from this engine generator, the effects of water-emulsified diesel fuel and loading on emission characteristics might be more clear. Understanding reduction of pollutant emissions during the use of water-emulsified diesel helps improve the effectiveness of the testing program. The analyzed consequences provide useful information to the government for setting policies to curb pollutant emissions from a light-duty diesel engine generator more effectively.     

Photocatalytic reduction of carbon dioxide to methanol and formic acid by graphene-TiO2

Graphene-TiO₂ was obtained by reduction of graphite oxide by the hydrothermal method. Using photocatalytic activity to reduce carbon dioxide to methanol and formic acid was investigated in this study. The results show that the graphene loading affects the absorption of light in the visible light region. A larger surface area can also improve the catalytic activity. The largest yield of methanol and formic acid, under light of 365 nm, can reach 160 and 150 μmol g^?1, respectively, with 8.5% graphene loading. An increase in graphene loading can enhance photocatalytic performance, but too much will also decrease the reduction efficiency by shielding the light from reaching the catalytic surface. The effect of pH was also investigated. The mechanism of the reaction was also discussed in this study.

Implications: Graphene-TiO₂ hybrids were prepared by the hydrothermal method. Surface area and visible light adsorption increased with the graphene loading. Increased graphene loading improved the methanol and formic acid production. Too much graphene loading will decrease the reduction efficiency. The effect of pH shows that the HCO₃^? species prefers the formation of formic acid. The mechanism of the reaction was also discussed in this study.     

An alternative supercritical fluid extraction system for aqueous matrices and its application in pesticides residue analysis

Abstract

Supercritical fluid extraction (SFE) is a rapid and convenient method for the isolation of organic compounds from environmental samples. This paper describes a supercritical carbon dioxide (CO₂) extraction system that uses a newly designed extraction cell to recover organic compounds from an aqueous matrix. Analysis of the extracts by gas chromatography‐electron capture detector (GC‐ECD) indicated that the herbicide trifluralin (2,6‐dinitro‐N,N‐dipropyl‐4‐trifluoromethylaniline) could be quantitatively extracted by using the SFE system proposed with small amounts of sample. The percentage of recovery obtained with the SFE system described was twice as high as the result obtained using a conventional solid‐phase extraction technique. Extraction by SFE was completed in a short period of time using a simple and low‐cost home‐made system that did not require the use of organic solvents.     

Sorption of 2,4-D on Natural and Organic Amended Soils of Different Characteristics

The effect of one organic amendment consisting of an urban waste compost (UWC) was assessed on the sorption properties of the herbicide 2,4-D on four soils of different physicochemical characteristics. The soils chosen were a Typic Haphorthod (ST), a Typic Endoaquept (SR), an Entic Pelloxerert (TO), and a Typic Eutrochrept (AL). Adsorption experiments were performed on the original soils, and on mixtures of these soils with UWC at a rate of 6.25% (w/w). These mixtures were used just after preparation, and after aging for 8 and 25 weeks. 2,4-D adsorption was the highest on ST soil, whereas the lowest adsorption was for SR soil. This behavior is related to the high amount of organic matter (OM) and amorphous iron and aluminum oxides content on soil ST, whereas soil SR had the lowest OM content and specific surface area of the soils of this study. Addition of exogenous OM to soils caused an increase in the 2,4-D adsorption by three of the soils treated with UWC, with the only exception being ST soil, due to an observed decrease in its specific surface area. The adsorbed amounts of the herbicide on aged organic fertilized soils diminished in three of the amended soils, but was still greater than on unamended soils. In contrast, the ST soil showed the largest adsorption for unamended soil.     

Coarsening of extracellularly biosynthesized cadmium crystal particles induced by thioacetamide in solution

A novel coarsening route for extracellularly biosynthesized cadmium nanocrystals was investigated for the first time. In this process, the white rot fungus Coriolus versicolor was employed to take up cadmium ions and synthesize extracellular cadmium crystal particles. The coarsening of the particles was induced by thioacetamide under certain conditions. Scanning electron microscopy showed that the formed cadmium crystal particles were coarsened from about 100 nm to 2-3 μm. The corresponding energy-dispersive X-ray spectra confirmed the presence of proteins in the particles. The maximum removal efficiency of Cd(II) increased from 17% to 87%, and the corresponding sorption capacity of biomass increased from 4 to 24 mg g⁻¹ with the completion of the coarsening process. The properties of the coarsened particles were also examined using X-ray diffraction (XRD) and transmission electron microscopy (TEM). XRD analysis of fungal mycelial pellets embedded with the coarsened particles confirmed the formation of cubic crystalline cadmium sulfide particles. The TEM results suggest that the coarsened particles were composed of clusters of several smaller particles. The changes in the functional groups on the biomass surface were studied through Fourier transform infrared spectroscopy. Based on the results above, a possible mechanism for the formation and coarsening of cadmium crystal particle is also discussed.