Herbicidal activity of slow-release herbicide formulations in wheat stands infested by weeds

The present study reports the herbicidal activity of metribuzin and tribenuron-methyl embedded in the degradable matrix of natural poly-3-hydroxybutyrate [P(3HB)/MET and P(3HB)/TBM]. The developed formulations were constructed as films and microgranules, which were tested against the weeds such as white sweet clover Melilotus albus and lamb's quarters Chenopodium album in the presence of soft spring wheat (Triticum aestivum, cv. Altaiskaya 70) as the subject crop for investigation. The activity was measured in laboratory scale experiments by determining the density and weight of the vegetative organs of weeds. The study was also aimed at testing the effect of the experimental formulation on the growth of wheat crop as dependent on the method of herbicide delivery. The experimental MET and TBM formulations showed pronounced herbicidal activity against the weed species used in the study. The effectiveness of the experimental formulations in inhibiting weed growth was comparable to and, sometimes, higher than that of the commercial formulations (positive control). The amount of the biomass of the wheat treated with the experimental herbicide formulations was significantly greater than that of the wheat treated with commercial formulations.     

Antifungal activity of P3HB microparticles containing tebuconazole

In this study, tebuconazole (TEB)-loaded poly-3-hydroxybutyrate (P3HB)-based microparticles were developed and comprehensively characterized. TEB-loaded microparticles with the initial loading amounts of the fungicide of 10, 25, and 50% of the polymer mass (TEB 10, TEB 25, and TEB 50%) were prepared using emulsion technique. Encapsulation efficiency of TEB varied from 59 to 86%. As the loading amount was increased, the average diameter of microparticles increased too, from 41.3 to 71.7?µm, while zeta potential was not influenced by TEB loading, varying between –32.6 and –35.7?mV. TEB was gradually released from the microparticles to the model medium, and after 60?d, from 25 to 43% of TEB was released depending on the content of the encapsulated fungicide. The data obtained from in vitro TEB release were fitted to different mathematical models. It was shown that the release profiles of TEB could be best explained by the Zero-order, Higuchi, and Hixson–Crowell models. The antifungal activity of the P3HB/TEB microparticles against phytopathogenic fungi Fusarium moniliforme and Fusarium solani was demonstrated by in vitro tests conducted in Petri dishes. Thus, hydrophobic agrochemicals (TEB) can be effectively encapsulated into P3HB microparticles to construct slow-release formulations.     

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.     

Kinetics of metribuzin release from bentonite-polymer composites in water

A series of bentonite polymer-composites (BPCs) loaded with metribuzin were studied for their controlled release in aqueous medium. The release of active ingredient from BPCs was significantly lower as compared to commercial metribuzin formulation. The results revealed that the cumulative metribuzin release was highest (81%) from the BPCs containing 8% clay (commercial bentonite) and 2% metribuzin which correspond to the lowest (14 days) half-life values i.e., time required for 50% release of active ingredient (t_1/2). The metribuzin release from the BPCs decreased with increased concentration of clays in polymer matrix and the release was further decreased with BPCs prepared with pure nano-bentonite. BPCs containing 12% clay and 2% metribuzin showed maximum t_1/2 values i.e., 25 and 51 days for commercial bentonite and pure nano-bentonite as clay sources, respectively. The differential behaviour in the metribuzin release rates from BPCs was ascribed due to variations in crosslinking of metribuzin in the composites. As metribuzin release was found to be slower in BPCs compared to commercial formulation, it could be used for control of weeds tailored to different crops.     

Controlled release formulations of metribuzin: Release kinetics in water and soil

Controlled release (CR) formulations of metribuzin in Polyvinyl chloride [(PVC) (emulsion)], carboxy methyl cellulose (CMC), and carboxy methyl cellulose-kaolinite composite (CMC-KAO), are reported. Kinetics of its release in water and soil was studied in comparison with the commercial formulation (75 DF). Metribuzin from the commercial formulation became non-detectable after 35 days whereas it attained maxima between 35–49 days and became non-detectable after 63 days in the developed products. Amongst the CR formulations, the release in both water and soil was the fastest in CMC and slowest in PVC. The CMC-KAO composite reduced the rate of release as compared to CMC alone. The diffusion exponent (n value) of metribuzin in water and soil ranged from 0.515 to 0.745 and 0.662 to 1.296, respectively in the various formulations. The release was diffusion controlled with half release time (t_1/2) from different controlled release matrices of 12.98 to 47.63 days in water and 16.90 to 51.79 days in soil. It was 3.25 and 4.66 days, respectively in the commercial formulation. The period of optimum availability of metribuzin in water and soil from controlled released formulations ranged from 15.09 to 31.68 and 17.99 to 34.72 days as against 5.03 and 8.80 days in the commercial formulation.     

Prevention of chloridazon and metribuzin pollution using lignin-based formulations

The herbicides chloridazon and metribuzin, identified as groundwater pollutants, were incorporated in lignin-based granules with different sizes to obtain controlled release formulations (CRFs) and reduce water pollution risk. Kinetics release tests in water and soil showed that the release rate of both from CRFs diminished in comparison to technical products. A linear correlation was obtained between the time taken for 50% of the active ingredient to be released (T₅₀) into water and granule size of the CRFs. Besides, a linear correlation was reached between T₅₀ values in water and soil. Mobility experiments carried out in calcareous soil show that the use of lignin-based CRFs reduces the presence of both herbicides in the leachate compared to the technical grade products. The set of experiments developed in this research can be useful to design, prepare and evaluate formulations with CR properties which can reduce the pollution derived from the use of herbicides.     

Development of controlled release nanoformulations of carbendazim employing amphiphilic polymers and their bioefficacy evaluation against Rhizoctonia solani

Controlled release nanoformulations of carbendazim (Methyl 1H-benzimidazol-2-ylcarbamate), a systemic fungicide, have been prepared using laboratory synthesized poly(ethylene glycols) (PEGs)-based functionalized amphiphilic copolymers. The release kinetics of carbendazim from developed controlled release (CR) formulations was studied and compared with that of the commercially available 50% Wettable Powder (WP). Further, the bioefficacy evaluation of developed formulations was done against plant pathogenic fungi Rhizoctonia solani by the poison food technique method. The release of maximum amount of carbendazim from developed formulations was dependent on the molecular weight of PEGs and was found to increase with increasing molecular weights. The range of carbendazim release was found to be between 10th to 35th day as compared to commercial formulation which was up to 7th day. The diffusion exponent (n value) of carbendazim in water ranged from 0.37 to 0.52 in the tested formulations. The half-release (t_1/2) values ranged between 9.47 and 24.20 days, and the period of optimum availability (POA) of carbendazim ranged from 9.15 to 26.63 days. Also, ED₅₀ values of the developed formulations vary from 0.40 to 0.74 mg L^?1. These formulations can be used to optimize the release of carbendazim to achieve disease control for the desired period depending on the matrix of the polymer used.     

Development of controlled release formulations of azadirachtin-A employing poly(ethylene glycol) based amphiphilic copolymers

Controlled release (CR) formulations of azadirachtin-A, a bioactive constituent derived from the seed of Azadirachta indica A. Juss (Meliaceae), have been prepared using commercially available polyvinyl chloride, polyethylene glycol (PEG) and laboratory synthesized poly ethylene glycol–based amphiphilic copolymers. Copolymers of polyethylene glycol and various dimethyl esters, which self assemble into nano micellar aggregates in aqueous media, have been synthesized. The kinetics of azadirachtin-A, release in water from the different formulations was studied. Release from the commercial polyethylene glycol (PEG) formulation was faster than the other CR formulations. The rate of release of encapsulated azadirachtin-A from nano micellar aggregates is reduced by increasing the molecular weight of PEG. The diffusion exponent (n value) of azadirachtin-A, in water ranged from 0.47 to 1.18 in the tested formulations. The release was diffusion controlled with a half release time (t_1/2) of 3.05 to 42.80 days in water from different matrices. The results suggest that depending upon the polymer matrix used, the application rate of azadirachtin-A can be optimized to achieve insect control at the desired level and period.     

Reduced Downward Mobility of Metolachlor and Metribuzin from Surfactant-Modified Clays

The study aims to prepare the organoclay complexes of metolachlor and metribuzin so as to reduce their downward mobility in soil profile. The organoclays were preadsorbed with phenyltrimethylammonium (PTMA) (50% of cation exchange capacity [CEC]) and hexadecyltrimethylammonium (HDTMA) (100% of CEC). Four metolachlor formulations, two for each organoclay, were prepared having 1% and 2% load of herbicide and were called PTMA-Metol-1%, PTMA-Metol-2%, HDTMA-Metol-1% and HDTMA-Metol-2%. Two metribuzin formulations were prepared and were called PTMA-Metri-1% and HDTMA-Metri-1%. Soil column leaching experiment showed that compared to their commercially available formulations, organoclay complexes were effective in reducing the downward mobility of both herbicides. Organoclay complexes of metolachlor and metribuzin prepared using PTMA-Montmorillonite performed better than the HDTMA-Montmorillonite complexes.     

Bio-efficacy evaluation of nanoformulations of β-cyfluthrin against Callosobruchus maculatus (Coleoptera: Bruchidae)

In the present investigation, bioefficacy of developed β-cyfluthrin formulations, utilizing laboratory synthesized poly(ethylene glycols) based amphiphilic copolymers, were evaluated against Callosobruchus maculatus (Coleoptera: Bruchidae). The bioefficacy data indicated that the formulations developed by utilizing polymers having PEG – 1500 (3c) and PEG – 2000 (3d) as the hydrophilic segment showed greater efficacy after 14 days as evident from EC₅₀ values (2.2 and 1.58 mg L^?1 respectively). Also, release from the commercial SC formulation was faster than developed formulations as the commercial formulation had the lowest EC₅₀ value on the first day (0.51 mg L^?1). The mean EC₅₀ of the commercial formulation against C. maculatus was quite high as compared to those of developed formulations. The results suggest that depending upon the polymer matrix used, the application rate of β-cyfluthrin can be optimized to achieve insect control at the desired level and period. The results described in this paper are promising and provide a comparison of developed formulations with the commercial one showing an earlier degradation of β-cyfluthrin in the latter and relatively prolonged activity in the former.     

Eco-friendly PEG-based controlled release nano-formulations of Mancozeb: Synthesis and bioefficacy evaluation against phytopathogenic fungi Alternaria solani and Sclerotium rolfsii

Controlled release (CR) nano-formulations of Mancozeb (manganese-zinc double salt of N,N-bisdithiocarbamic acid), a protective fungicide, have been prepared using laboratory-synthesized poly(ethylene glycols) (PEGs)-based functionalized amphiphilic copolymers without using any surfactants or external additives. The release kinetics of the developed Mancozeb CR formulations were studied and compared with that of commercially available 42% suspension concentrate and 75% wettable powder. Maximum amount of Mancozeb was released on 42nd day for PEG-600 and octyl chain, PEG-1000 and octyl chain, and PEG-600 and hexadecyl chain, on 35th day for PEG-1000 and hexadecyl chain, on 28th day for PEG-1500 and octyl chain, PEG-2000 and octyl chain, PEG-1500 and hexadecyl chain, and PEG-2000 and hexadecyl chain in comparison to both commercial formulations (15th day). The diffusion exponent (n value) of Mancozeb in water ranged from 0.42 to 0.62 in tested formulations. The half-release (t_1/2) values ranged from 17.35 to 35.14 days, and the period of optimum availability of Mancozeb ranged from 18.54 to 35.42 days. Further, the in vitro bioefficacy evaluation of developed formulations was done against plant pathogenic fungi Alternaria solani and Sclerotium rolfsii by poison food technique. Effective dose for 50% inhibition in mgL^?1 (ED₅₀) values of developed formulations varied from 1.31 to 2.79 mg L^?1 for A. solani, and 1.60 to 3.14 mg L^?1 for S. rolfsii. The present methodology is simple, economical, and eco-friendly for the development of environment-friendly CR formulations of Mancozeb. These formulations can be used to optimize the release of Mancozeb to achieve disease control for the desired period depending upon the matrix of the polymer used. Importantly, the maximum amount of active ingredient remains available for a reasonable period after application. In addition, the developed CR formulations were found to be suitable for fungicidal applications, allowing use of Mancozeb in lower doses.     

Reduced downward mobility of metolachlor and metribuzin from surfactant-modified clays

The study aims to prepare the organoclay complexes of metolachlor and metribuzin so as to reduce their downward mobility in soil profile. The organoclays were preadsorbed with phenyltrimethylammonium (PTMA) (50% of cation exchange capacity [CEC]) and hexadecyltrimethylammonium (HDTMA) (100% of CEC). Four metolachlor formulations, two for each organoclay, were prepared having 1% and 2% load of herbicide and were called PTMA-Metol-1%, PTMA-Metol-2%, HDTMA-Metol-1% and HDTMA-Metol-2%. Two metribuzin formulations were prepared and were called PTMA-Metri-1% and HDTMA-Metri-1%. Soil column leaching experiment showed that compared to their commercially available formulations, organoclay complexes were effective in reducing the downward mobility of both herbicides. Organoclay complexes of metolachlor and metribuzin prepared using PTMA-Montmorillonite performed better than the HDTMA-Montmorillonite complexes.     

Release behavior and bioefficacy of imazethapyr formulations based on biopolymeric hydrogels

Controlled release formulations of imazethapyr herbicide have been developed employing guar gum-g-cl-polyacrylate/bentonite clay hydrogel composite (GG-HG) and guar gum-g-cl-PNIPAm nano hydrogel (GG-NHG) as carriers, to assess the suitability of biopolymeric hydrogels as controlled herbicide release devices. The kinetics of imazethapyr release from the developed formulations was studied in water and it revealed that the developed formulations of imazethapyr behaved as slow release formulations as compared to commercial formulation. The calculated diffusion exponent (n) values showed that Fickian diffusion was the predominant mechanism of imazethapyr release from the developed formulations. Time for release of half of the loaded imazethapyr (t_1/2) ranged between 0.06 and 4.8 days in case of GG-NHG and 4.4 and 12.6 days for the GG-HG formulations. Weed control index (WCI) of GG-HG and GG-NHG formulations was similar to that of the commercial formulation and the herbicidal effect was observed for relatively longer period. Guar gum-based biopolymeric hydrogels in both macro and nano particle size range can serve as potential carriers in developing slow release herbicide formulations.     

Impact of soil amendments on metribuzin and DCPA half-lives and mobility into agricultural runoff water

The retention and behavior of two herbicides, metribuzin [4-amino-6-tert-butyl-4, 5-dihydro-3-methylthio-1, 2, 4-triazin-5-one] and DCPA [1, 4-Benzenedicarboxylic acid, 2, 3, 5, 6-tetrachloro-, dimethyl] ester, in runoff and seepage water from agricultural fields were investigated. The objectives of this investigation were to: (i) determine the dissipation and half-life (T _1/2) of metribuzin and DCPA herbicides in soil under three management practices: chicken manure (CM), sewage sludge (SS), and no-mulch native soil (NM); (ii) monitor herbicides residues in runoff and infiltration water following addition of soil amendments; and (iii) determine the impact of soil amendments on the transport of NO₃, NH₄, and PO₄ from soil into surface and subsurface water. Half-life (T _1/2) values of metribuzin were 24, 18, and 12 d in CM, SS, and NM treatments, respectively. Similarly, T _1/2 values of DCPA were greater in CM and SS incorporated soil (45.8 and 52.2 d, respectively) compared to NM native soil (26.2 d). Addition of CM and SS to native agricultural soil increased water infiltration, lowering runoff water volume and herbicide residues in runoff following natural rainfall events. We concluded that soil amendments could be used to intercept pesticide-contaminated runoff from agricultural fields. This practice might provide a potential solution to pesticide contamination of surface and seepage water from farmlands.     

Controlled-release formulations of cyromazine-lignin matrix coated with ethylcellulose

An encapsulation system was developed and designed to give long-lasting effectiveness of the insect growth regulator cyromazine. Cyromazine was incorporated in lignin-poly (ethylene glycol) (PE) controlled-release formulations by means of a melting process. The basic formulation [lignin (65%)–PE (20%)–cyromazine (15%)] was coated in a Wurster-type fluidized-bed equipment using two different amounts of ethylcellulose. That of the highest one was modified by the addition of a plasticizer, dibutyl sebacate (DBS). The effect on cyromazine release rate caused by the incorporation of ethylcellulose and DBS in lignin-PE formulation was studied by immersion of the granules in water under static conditions. Using an empirical equation, the time taken for 50% of the active ingredient to be released into water (T₅₀) was calculated. From the analysis of the T₅₀ values, the influence of ethylcellulose appears clearly defined, observing a delay in release rate of cyromazine with respect to the basic lignin-PE formulation. In addition, the granules coated with ethylcellulose and the plasticizer lead the slowest release rate into water. The release of cyromazine into water is controlled by a diffusion mechanism. The thickness and permeability of the coating film are the most important factors that affect cyromazine release.     

Development of controlled release formulations of carbofuran and imidacloprid and their bioefficacy evaluation against aphid,Aphis gossypii and leafhopper,Amrasca biguttula biguttula Ishida on potato crop

Controlled release (CR) formulations of carbofuran and imidacloprid were prepared employing polyvinyl chloride and carboxymethyl cellulose (CMC) and their bioefficacy was evaluated against the aphid, Aphis gossypii and leafhopper, Amrasca biguttula biguttula Ishida on potato crop. The CR formulations of carbofuran and imidacloprid provided better or equal control of the pests than commercial formulations. CMC-based formulation provided a superior control of both the pests. The Imida-CMC, which showed the lowest population of leaf hopper (10.50 leafhopper/100 cl), provided significantly superior control among all treatments after 35 days after germination (DAG). The residue of carbofuran and imidacloprid in potato tuber and soils were not detectable at the time of harvesting in any one of the formulations.     

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.     

Degradation of Metribuzin in Two Soil Types of Lebanon

The degradation of metribuzin [4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5(4H)-one] as influenced by soil type, temperature, humidity, organic fertilizers, soil sterilization, and ultra-violet radiation was studied in two soil types of Lebanon under laboratory conditions. The two soil types were sandy loam and clay. Deamination of metribuzin in the sandy loam soil to its deaminometribuzin (DA) derivative was basically a result of biological activity. In the clay soil the first metabolite diketometribuzin (DK) was a result of oxidative desulfuration, while diketo-deaminometribuzin (DADK) was the product of reductive deamination. The two soils represented major differences in the pesticide transformation processes. Photodecomposition on the soil surface and in aqueous media was also an important process in the degradation of metribuzin. Furthermore, the increase in soil organic matter enhanced degradation.     

Comparative assessment of metribuzin sorption efficiency of biochar,hydrochar and vermicompost

Abstract

In this study, we used two biochars (BC) produced from grapevine pruning residues (BCgv) and red spruce wood (BCrs), two hydrochars (HC) from urban pruning residues (HCup) and the organic fraction of municipal solid wastes (HCuw), and two vermicomposts (VC) obtained vermicomposting digestates from buffalo manure (VCbm) and mixed feedstock (VCmf). Adsorption kinetics and isotherms of metribuzin onto these materials were performed. Sorption kinetics followed preferentially a pseudo-second-order model, thus indicating the occurrence of chemical interactions between the sorbate and the adsorbents. Adsorption constants were calculated using the Freundlich and Langmuir models. Metribuzin sorption data on BCgv and both HC fitted preferentially the Freundlich equation, whereas on the other materials data fitted both isotherms well (r?>?0.95). Metribuzin sorption capacity of the materials followed the trend BC?>?HC?>?VC. Sorption constants of metribuzin normalised per organic carbon content (K_OC) on BCgv, BCrs, HCup, HCuw, VCbm and VCmf were 561, 383, 251, 214, 102 and 84?L kg^?1, respectively. A significant positive correlation (P?=?0.016) was calculated between distribution coefficients (K_d) of all materials and the corresponding organic carbon contents, thus indicating a prominent role of the organic fraction of these materials in the adsorption of metribuzin.