Controlled release systems to prevent the agro-environmental pollution derived from pesticide use

Different controlled release formulations (CRFs) of isoproturon, imidacloprid and cyromazine have been studied to contribute to diminish, somehow, the problems related to the application of conventional formulations. The alginate-based CRFs were based on sodium alginate (1.90%), Technical grade (TG) isoproturon or imidacloprid (1.20%), natural bentonite (3.30%), and water (93.6%), and the lignin-based CRF was based on kraft lignin (50.0%) and TG cyromazine (50.0%). The mobility of non-formulated TG pesticides and CRFs were compared by using soil columns. The use of CRFs retard release and reduce the presence of pesticides in the leachate and, moreover, the pesticides stay in the soil longer. Sorption capacity of the soil for pesticides was measured using batch experiments. The results obtained (11.67 mg kg(- 1) for isoproturon, 3.17 mg kg(- 1) for imidacloprid and 0.63 mg kg(-1) for cyromazine) were in agreement with those obtained under dynamic conditions.     

Controlled release systems to prevent the agro-environmental pollution derived from pesticide use

Different controlled release formulations (CRFs) of isoproturon, imidacloprid and cyromazine have been studied to contribute to diminish, somehow, the problems related to the application of conventional formulations. The alginate-based CRFs were based on sodium alginate (1.90%), Technical grade (TG) isoproturon or imidacloprid (1.20%), natural bentonite (3.30%), and water (93.6%), and the lignin-based CRF was based on kraft lignin (50.0%) and TG cyromazine (50.0%). The mobility of non-formulated TG pesticides and CRFs were compared by using soil columns. The use of CRFs retard release and reduce the presence of pesticides in the leachate and, moreover, the pesticides stay in the soil longer. Sorption capacity of the soil for pesticides was measured using batch experiments. The results obtained (11.67 mg kg^{? 1} for isoproturon, 3.17 mg kg^{? 1} for imidacloprid and 0.63 mg kg^?1 for cyromazine) were in agreement with those obtained under dynamic conditions.     

热改性净水污泥对水体底泥磷的控释机制

本研究以净水污泥为原料,通过400 ℃、4 h煅烧制备了热改性净水污泥。探讨了其对水体中磷酸盐的吸附特性,以及在不同投加量 (2.5%、5%、10%) 下热改性净水污泥对底泥中磷的控释及形态影响。同时结合SEM、BET等表征手段,探究了WTS_400-4对底泥中磷的稳定机理。结果表明,WTS_400-4相比WTS具有更发达的孔隙结构及比表面积,增强了对磷酸盐的吸附能力。吸附过程符合准二级动力学模型,Freundlich模型更适用于描述WTS_400-4吸附磷酸盐的过程,其中参数n＞1,说明WTS_400-4对磷酸盐的吸附容易进行。WTS_400-4的添加会使底泥中弱吸附态磷(NH₄Cl-P)、氧化还原敏感态磷(BD-P)和有机磷(Org-P)等不稳定态磷向稳定的金属氧化物结合态磷(NaOH-rP)转变,且其转化量会随着WTS_400-4投加量的增加而增加,有助于抑制底泥磷向上覆水释放。此外,WTS_400-4的添加可降低底泥中WSP(水溶性磷)和Olsen-P (碳酸氢钠可提取磷)这2种生物有效磷含量。WTS_400-4添加入底泥,一方面可以降低底泥中潜在活性磷和生物有效磷含量,降低底泥内源磷向上覆水释放的风险,另一方面可以通过WTS_400-4的吸附作用直接去除间隙水中的磷,从而降低上覆水和间隙水之间的磷浓度梯度,进而抑制磷从间隙水向上覆水中释放。结果表明,WTS_400-4可作为底泥改良剂用以控制水体和底泥的磷含量。     

Development of controlled release formulations of thiram employing amphiphilic polymers and their bioefficacy evaluation in seed quality enhancement studies

Controlled release formulations of Thiram (Dimethylcarbamothioylsulfanyl-N,N-dimethylcarbamodithioate), a contact fungicide, have been prepared using laboratory synthesized poly(ethylene glycol) (PEG) based functionalized amphiphilic copolymers. The kinetics of thiram from developed controlled release (CR) formulations were studied in comparison with that of the commercially available 75 WS. Release from the commercial formulation was faster than with the developed CR formulations. Maximum amount of thiram was released on 35th day for PEG-2000 4d, 28th day for PEG-1500 4c, 21st day for PEG-1000 4b and 15th day for PEG-600 4a in comparison to commercial formulation (7th day). The diffusion exponent (n) of thiram in water ranged from 0.356 to 0.545 in the tested formulations. The half-release (t_1/2) values ranged between 14.78 to 22.1 days, and the Period of Optimum Availability (POA) of thiram ranged from 7.79 to 25.15 days. An effort has also been made to identify the suitable polymers that could reduce the seed deterioration during storage and also act as an effective carrier of fungicide thiram. The results demonstrate that the seeds coated with the different formulations deteriorated at a slower pace as manifested in high germination percentage over control. Apart from the fungicidal effect of thiram, the polymers acted as barriers to moisture reducing the rate of seed deterioration and checked the degradation of thiram. The CR formulation 4d, with PEG 2000, was found to be most effective as seed coat.     

控制释放技术与水的消毒保质

介绍了控制释放技术及其在水消毒保质方面的应用 ,指出了控制释放技术在水消毒保质方面的优越性、重要意义及应用前景     

Controlled release, blind test of DNAPL remediation by ethanol flushing

A dense nonaqueous phase liquid (DNAPL) source zone was established within a sheet-pile isolated cell through a controlled release of perchloroethylene (PCE) to evaluate DNAPL remediation by in-situ cosolvent flushing. Ethanol was used as the cosolvent, and the main remedial mechanism was enhanced dissolution based on the phase behavior of the water-ethanol-PCE system. Based on the knowledge of the actual PCE volume introduced into the cell, it was estimated that 83 L of PCE were present at the start of the test. Over a 40-day period, 64% of the PCE was removed by flushing the cell with an alcohol solution of approximately 70% ethanol and 30% water. High removal efficiencies at the end of the test indicated that more PCE could have been removed had it been possible to continue the demonstration. The ethanol solution extracted from the cell was recycled during the test using activated carbon and air stripping treatment. Both of these treatment processes were successful in removing PCE for recycling purposes, with minimal impact on the ethanol content in the treated fluids. Results from pre- and post-flushing partitioning tracer tests overestimated the treatment performance. However, both of these tracer tests missed significant amounts of the PCE present, likely due to inaccessibility of the PCE. The tracer results suggest that some PCE was inaccessible to the ethanol solution which led to the inefficient PCE removal rates observed. The flux-averaged aqueous PCE concentrations measured in the post-flushing tracer test were reduced by a factor of 3 to 4 in the extraction wells that showed the highest PCE removal compared to those concentrations in the pre-flushing tracer test.     

Controlled release,blind tests of DNAPL characterization using partitioning tracers

The partitioning tracer technique for dense nonaqueous phase liquid (DNAPL) characterization was evaluated in an isolated test cell, in which controlled releases of perchloroethylene (PCE) had occurred. Four partitioning tracer tests were conducted, two using an inverted, double five-spot pumping pattern, and two using vertical circulation wells. Two of the four tests were conducted prior to remedial activities, and two were conducted after. Each test was conducted as a "blind test" where researchers conducting the partitioning tracer tests had no knowledge of the volume, method of release, nor resulting spatial distribution of DNAPL. Multiple partitioning tracers were used in each test, and the DNAPL volume estimates varied significantly within each test based on the different partitioning tracers. The tracers with large partitioning coefficients generally predicted a smaller volume of PCE than that expected based on the actual release volume. However, these predictions were made for low DNAPL saturations (average saturation was approximately 0.003), under conditions near the limits of the method's application. Furthermore, there were several factors that may have hindered prediction accuracy, including tracer degradation and remedial fluid interference.     

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.     

Review of strobilurin fungicide chemicals

Strobilurins are natural products isolated and identified from specific fungi. Natural strobilurins were named in the order of their discovery as strobilurin-A followed by strobilurin-B, C, D etc. Their discovery opened the door for new chemistry of synthetic fungicides. Applying Quantitative Structural Activity Relationship (QSAR) on the structures of the natural strobilurins, many pesticide companies were able to discover many synthetic analogues that are more efficacious and more stable fungicides. At present there are about eight synthetic strobilurins in the fungicides worldwide market. Some of these products are worldwide registered for use as agrochemical and some are in the process of registration. This class of fungicides is relatively new, as crop protection products and information about them is still fairly scarce. In this review, syntheses and chemistry of natural and synthetic strobilurins are discussed. Also, the mode of action, efficacy, biotic/abiotic degradation, analytical methods, and agricultural uses are discussed.     

Transfer of the fungicide vinclozolin from treated to untreated plants via volatilization

Head lettuce plantlets (Lactuca sativa L. var. capitata) were potted, treated with vinclozolin at the six-leaf stage according to application standards and allowed to dry for 24 h. The potted plantlets were then placed in either growth chambers with controlled temperature (20 and 25 degrees C, respectively) or in a greenhouse (approximately 12 degrees C), together with untreated spinach (Spinacia oleracea L.) and standardized grass cultures (Lolium multiflorum Lam. ssp.) While the treated lettuce pots remained in the respective growing compartments until the end of the experiments, spinach and grass were exposed to the compartment air for 24 h and their shoot material was analyzed for vinclozolin by GC-ECD and GC-high resolution mass spectrometry. Exposure and analysis of untreated spinach and grass were carried out at two- or three-day intervals during the course of the experiments. Also, air samples were taken from the compartments at intervals and analyzed for vinclozolin. Maximum vinclozolin concentration in the growth chamber air was about 330 ng m(-3) while vinclozolin contamination of the untreated plants ranged from 50 to 200 microg kg(-1) FW (fresh weight). In the greenhouse atmospheric vinclozolin concentration reached approximately 15 ngm(-3) and maximum contamination of spinach and grass were 30-40 microg kg(-1) FW. Our data clearly show that unintended contamination of plants growing in the vicinity of vinclozolin-treated plants can occur even if the fungicide layer is completely dry. Implications for safety testing and food plants are discussed.     

Review of strobilurin fungicide chemicals

Strobilurins are natural products isolated and identified from specific fungi. Natural strobilurins were named in the order of their discovery as strobilurin-A followed by strobilurin-B, C, D etc. Their discovery opened the door for new chemistry of synthetic fungicides. Applying Quantitative Structural Activity Relationship (QSAR) on the structures of the natural strobilurins, many pesticide companies were able to discover many synthetic analogues that are more efficacious and more stable fungicides. At present there are about eight synthetic strobilurins in the fungicides worldwide market. Some of these products are worldwide registered for use as agrochemical and some are in the process of registration. This class of fungicides is relatively new, as crop protection products and information about them is still fairly scarce. In this review, syntheses and chemistry of natural and synthetic strobilurins are discussed. Also, the mode of action, efficacy, biotic/abiotic degradation, analytical methods, and agricultural uses are discussed.     

Microbial conversion of fungicide vinclozolin

An ecological safety study of using vinclozolin in field and laboratory experiments showed that the effect of the preparation led to a decrease in the abundance of actinomycetes and mycelial fungi and an enhancement of nitrification. The residual amounts of vinclozolin in soil after 12 months were 6-12% of the dose introduced. The persistent chlorinated derivatives of the toxicant were found. Microbial strains pertaining to the genera Pseudomonas and Bacillus were isolated that utilized vinclozolin as the sole source of carbon and energy.     

Sensitized photooxygenation of the fungicide furalaxyl

BACKGROUND: The photolysis of pesticides is of high current interest since light is one of the most important abiotic factors which are responsible for the environmental fate of these substances and may induce their conversion into noxious products. The action of light can also be mediated by oxygen and synthetic or naturally occurring substances which act as sensitizers. Our objective in this study was to investigate the photochemical behaviour of the systemic fungicide furalaxyl in the presence of oxygen and various sensitizers, and to compare the toxicity of the main photoproduct(s) to that of the parent compound. Previous reports on the direct photolysis of the pesticide demonstrated a very slow degradation and the only identified photoproducts were N-2,6-xylyl-D,L-alaninare and 2,6-dimethylaniline. METHODS: Solutions of furalaxyl in CH3CN were photooxygenate using a 500W high-pressure mercury lamp (through a Pyrex glass filter, lambda>300 nm) or a 650W halogen lamp or sunlight and the proper sensitizer. When sunlight was used, aqueous solutions were employed. The photodegradation was checked by NMR and/or GC-MS. The photoproducts were spectroscopically evidenced and, when possible, isolated chromatographically. Acute toxicity tests were performed on the rotifer Brachionus calyciflorus, the crustacean cladoceran Daphnia magna and the anostracan Thamnocephalus platyurus, while chronic toxicity tests (sublethal endpoints) comprised a producer, the alga Pseudokirchneriella subcapitata and the crustacean Ceriodaphnia dubia, as a consumer. RESULTS AND DISCUSSION: In the presence of both oxygen and sensitizer, furalaxyl underwent rapid photochemical transformations mainly to N-disubstituted formamide, maleic anhydride and a 2(5H)-furanone derivative. The formation of these products was rationalized in terms of a furan endoperoxide intermediate derived from the reaction of furalaxyl with active dioxygenated species (singlet oxygen, superoxide anion or ground state oxygen). The 2(5H)-furanone exhibited a higher toxicity than the parent compound. CONCLUSION: This work reports the first data on the photosensitized oxygenation of furalaxyl with evidence of the high tendency of the pesticide to undergo photodegradation under these conditions leading, among other things, to a 2(5H)-furanone, which is more toxic than the starting furalaxyl towards aquatic organisms. RECOMMENDATIONS AND OUTLOOK: Investigation highlights that the photolytic fate of a pesticide, although quite stable to direct photoreaction due to its low absorption of solar radiation at ground level, can be significantly influenced in the environment by the presence of substances with energy or electron-transfer properties as natural dyes, e.g. chlorophyll, or synthetic pollutants, e.g. polycyclic aromatic hydrocarbons (PAH).     

Spectrophotometric determination of the fungicide captan

A spectrophotometric method for the determination of the fungicide captan has been developed based on its reaction with thiosemicarbazide. The absorbance was measured at 315 nm. The effects of the proportion of water, thiosemicarbazide concentration, pH and temperature on this reaction was studied to select the best chemical conditions. The calibration graph was obtained between 1.2 and 30 ppm and the detection limit is 0.5 ppm. The RSD (n = 10) was 1.34%. Possible interference of various pesticides was examined. The method was applied to the determination of captan in agrochemical formulations. Results agree well with the labelled values and also with results that were obtained by a polarographic method.     

Photochemical behaviour of the systemic fungicide carboxin

Irradiation of carboxin (1) with a 500 W UV lamp (filter Pyrex) in CH3CN leads to the products 3, 5-8, 12-14 depending upon the reaction conditions. All photo-products were isolated and characterized. Photooxidation occurred even if unsensitized, while photoalteration was very slow in the absence of oxygen. The main oxygenated-products 3 and 13 were also recovered under biomimetic conditions by exposure of an aqueous solution of 1 to sunlight.     

底泥污染物释放动力学研究

采用模拟试验方式和新型微生物数量测定方法 ,研究了沼泽化湖泊底泥和受污染河流底泥在不同扰动状态下 ,底泥耗氧速率、氮和磷污染物释放动力学过程。结果表明 :( 1)底泥耗氧速率是同样条件下上覆水耗氧速率的 48倍 ,而在扰动状态下 ,底泥耗氧速率达到上覆水耗氧速率的 5 96— 93 6倍 ,扰动底泥显著增大其耗氧速率 ,底泥污染越严重 ,其耗氧速率越大 ,对水体产生的影响也越大。 ( 2 )扰动底泥可以显著增大底泥的氮磷释放速率 ,氮的释放受有机氮的氨化、氨氮的硝化、硝酸盐氮的反硝化以及氨氮被微生物吸收转化为有机氮等的影响 ;磷的释放过程受厌氧过程和底泥颗粒吸附的影响 ,耗氧速率高的底泥具有更大的氮磷释放潜力。 ( 3 )微生物数量在底泥污染物释放动力学中起着关键性作用 ,新型方法可以快速检测微生物总量。试验结果对于水环境的管理、受污染水体的修复 ,以及底泥的处理处置等都具有重要的指导意义     

Controlled release and retarded leaching of pesticides by encapsulating in carboxymethyl chitosan /bentonite composite gel

A novel composite gel composed of carboxymethyl-chitosan (CM-chit) and bentonite (H-bent) was used as the carrier for encapsulating atrazine and imidacloprid to control their release in water and retard their leaching in soil. Strong interactions between CM-chit and H-bent in the composite were confirmed by FT-IR, and good dispersion of pesticides in the carrier was observed by SEM. According to the results of release experiments in water, the CM-chit/H-bent composite carrier showed double advantages of both encapsulation by the polymer and sorption by the bentonite. The time taken for 50 % of active ingredients to be released, t ₅₀, was prolonged to 572 h for atrazine and 24 h for imidacloprid, respectively. The difference between the two pesticides on release behavior was related to their hydrophobicity and water solubility. Leaching experiments through a soil layer showed that this novel carrier reduced the amount of pesticides available for leaching, and would be useful for diminishing the environmental pollution of pesticides.     

Controlled release and retarded leaching of pesticides by encapsulating in carboxymethyl chitosan /bentonite composite gel

A novel composite gel composed of carboxymethyl-chitosan (CM-chit) and bentonite (H-bent) was used as the carrier for encapsulating atrazine and imidacloprid to control their release in water and retard their leaching in soil. Strong interactions between CM-chit and H-bent in the composite were confirmed by FT-IR, and good dispersion of pesticides in the carrier was observed by SEM. According to the results of release experiments in water, the CM-chit/H-bent composite carrier showed double advantages of both encapsulation by the polymer and sorption by the bentonite. The time taken for 50 % of active ingredients to be released, t??, was prolonged to 572 h for atrazine and 24 h for imidacloprid, respectively. The difference between the two pesticides on release behavior was related to their hydrophobicity and water solubility. Leaching experiments through a soil layer showed that this novel carrier reduced the amount of pesticides available for leaching, and would be useful for diminishing the environmental pollution of pesticides.