Remediation of s-triazines contaminated water in a laboratory scale apparatus using zero-valent iron powder

Atrazine, propazine and simazine were tested separately and in mixture by batch procedure in a laboratory-constructed apparatus. 3.75 l of a buffered s-triazines pesticide solution was treated at room temperature by 325-mesh zero-valent iron powder (ZVIP) (20 g/l). High performance liquid chromatography was used to separate by-products and study the decline in the pesticide’s concentrations. Results obtained show that the order of degradation was simazine, atrazine and then propazine. The half-lives (t_1/2) of the s-triazines pesticides are, respectively, 7.4, 9.0 and 10.6 min when they are treated separately, and 9.8, 11.2 and 13.7 min when they are treated together under the same conditions. The final by-product obtained after 50 min of contact of simazine with ZVIP shows a shift to longer wavelength in its UV spectrum. A similar phenomenon is shown for atrazine and propazine. Identical primary by-products are produced and subsequently degraded to 4,6-(diamino)-s-triazine, which seems to be the major by-product of the reductive treatment process. Pathways for the degradation of the studied s-triazines by ZVIP are proposed.     

Remediation of s-triazines contaminated water in a laboratory scale apparatus using zero-valent iron powder

Atrazine, propazine and simazine were tested separately and in mixture by batch procedure in a laboratory-constructed apparatus. 3.75 l of a buffered s-triazines pesticide solution was treated at room temperature by 325-mesh zero-valent iron powder (ZVIP) (20 g/l). High performance liquid chromatography was used to separate by-products and study the decline in the pesticide’s concentrations. Results obtained show that the order of degradation was simazine, atrazine and then propazine. The half-lives (t_1/2) of the s-triazines pesticides are, respectively, 7.4, 9.0 and 10.6 min when they are treated separately, and 9.8, 11.2 and 13.7 min when they are treated together under the same conditions. The final by-product obtained after 50 min of contact of simazine with ZVIP shows a shift to longer wavelength in its UV spectrum. A similar phenomenon is shown for atrazine and propazine. Identical primary by-products are produced and subsequently degraded to 4,6-(diamino)-s-triazine, which seems to be the major by-product of the reductive treatment process. Pathways for the degradation of the studied s-triazines by ZVIP are proposed.     

Predictability by Box-Behnken model for carbaryl adsorption by soils of Indian origin

This study was undertaken to investigate the adsorption capacity of carbaryl on four Indian soils with different physiochemical properties. A batch adsorption study was carried out in order to evaluate the maximum adsorption capacity of carbaryl using a Response Surface Methodology (RSM). The effects of operating parameter such as initial carbaryl concentration (1–20 mgL^?1), adsorbent dosage (0.5–6 g) and contact time (10–180 min) were examined. The proposed quadratic model for Box-Behnken design fits very well to the experimental data because it may be used to navigate design space according to ANOVA results. The regression co-efficient (R²) of the models developed and the results of validation experiments conducted at optimal conditions strongly suggests that the predicted values are in good agreement with experimental results. Contour and response surface plots are used to determine the interactions effects of main factors and optimal conditions of the process. The experiment can be utilized as a guideline for better understanding of carbaryl adsorption onto soil under different operating conditions. The results show that the forest soil is most efficient in binding carbaryl (Sevin) than the other types of soil tested.     

Degradation of benomyl, picloram, and dicamba in a conical apparatus by zero-valent iron powder

Reduction of some pesticides (benomyl, picloram, and dicamba) was studied in an aerobic batch conical pilot system to investigate the disappearance of these pesticides on contact with iron powder (20 g/l, 325-mesh). Aqueous buffered solutions of the compounds were added to the system followed by zero-valent iron powder (ZVIP), and the decline in the pesticide concentrations was monitored over time. HPLC analyses show a complete disappearance of picloram (1.20 mg/l) after 20 min of reaction. Benomyl (1.00 mg/l) and dicamba (1.25 mg/l) disappear after 25 and 40 min, respectively. The t₅₀ values ranged from 3 to 5.5 min, and were about slightly less than the t_1/2 values reported when the log of the relative HPLC peak area was plotted versus time, where the relative peak area was calculated by dividing the measured peak area by the initial peak area. Pathways for the degradation of the studied pesticides by ZVIP are proposed.     

Dissipation of carbofuran and carbaryl on Oolong tea during tea bushes,manufacturing and roasting processes

Carbofuran (2,3-dihydro-2,2-dimethyl-7-benzofuranol-N-methylcarbamate) and carbaryl (1-naphthyl-N-methylcarbamate) are insecticides widely used in tea plantations. The objective of the present study was to evaluate the dissipation of carbofuran and carbaryl during the growth periods of Oolong tea, processing and roasting. Analysis of the residual insecticides was carried out using high-pressure liquid chromatography with a post-column fluorescence detector. Results showed that in the tea field carbofuran dissipated faster then carbaryl. Manufacturing processes of Oolong tea further reduced the carbofuran and carbaryl contents. The persistence of carbofuran and carbaryl was decreased with increasing roasting temperature. From the results, we conclude that the presence of carbofuran and carbaryl in tea can be reduced by proper field management, manufacturing and roasting processes.     

Dissipation of carbofuran and carbaryl on Oolong tea during tea bushes, manufacturing and roasting processes

Carbofuran (2,3-dihydro-2,2-dimethyl-7-benzofuranol-N-methylcarbamate) and carbaryl (1-naphthyl-N-methylcarbamate) are insecticides widely used in tea plantations. The objective of the present study was to evaluate the dissipation of carbofuran and carbaryl during the growth periods of Oolong tea, processing and roasting. Analysis of the residual insecticides was carried out using high-pressure liquid chromatography with a post-column fluorescence detector. Results showed that in the tea field carbofuran dissipated faster then carbaryl. Manufacturing processes of Oolong tea further reduced the carbofuran and carbaryl contents. The persistence of carbofuran and carbaryl was decreased with increasing roasting temperature. From the results, we conclude that the presence of carbofuran and carbaryl in tea can be reduced by proper field management, manufacturing and roasting processes.     

Effects of droplet density and concentration on the efficacy of bacillus thuringiensis and carbaryl against gypsy moth larvae (Lymantria dispar L.)

Abstract

The feeding behavior of gypsy moth larvae exposed to two pesticide deposits (Bt and carbaryl) on oak leaf disks was monitored to determine the relationships between its efficacy and application parameters (droplet density and pesticide concentration). A range of pesticide concentrations and droplet densities (from 9 to 149 droplets/cm²) was used to simulate high and low application rates produced by different methods of application in the field.

The LD₅₀ and the LC₅₀, appeared to be affected by the spatial distribution of the deposit on the leaf surface. Both Bt and carbaryl showed a decreasing LD₅₀ at increasing time after spray. The LD₅₀ of Bt decreased from 14.1 BIU/liter to 3.1 BIU/Iiter between 48 and 144 hours after spray. The results show that feeding inhibition by Bt is more closely related to concentration than to droplet density and dose per unit area with the highest feeding inhibition occurring at 10 BIU/liter at 9 droplets/cm². With carbaryl, an increase in both concentration and droplet density was necessary to cause a decrease in leaf area eaten by larvae.     

Effect of carbaryl (carbamate insecticide) on acetylcholinesterase activity of two strains of Daphnia magna (Crustacea,Cladocera)

The present study was designed to investigate the effect of carbaryl (carbamate insecticide) on the acetylcholinesterase activity in two strains (same clone A) of the crustacean cladoceran Daphnia magna. Four carbaryl concentrations (0.4, 0.9, 1.8 and 3.7 µg L^?1) were compared against control AChE activity. Our results showed that after 48 h of carbaryl exposure, all treatments induced a significant decrease of AChE activities whatever the two considered strains. However, different responses were registered in terms of lowest observed effect concentrations (LOEC: 0.4 µg L^?1 for strain 1 and 0.9 µg L^?1 for strains 2) revealing differences in sensitivity among the two tested strains of D. magna. These results suggest that after carbaryl exposure, the AChE activity responses can be also used as a biomarker of susceptibility. Moreover, our results show that strain1 is less sensitive than strain 2 in terms of IC50-48 h of AChE activity. Comparing the EC50-48 h of standard ecotoxicity test and IC50-48 h of AChE inhibition, there is the same order of sensitivity with both strains.     

Effects of long- and short-term exposure to carbaryl on survival, growth and reproduction of Daphnia ambigua

In laboratory experiments a cladoceran, Daphnia ambigua, was exposed for six instars to the insecticide carbaryl at five different concentrations (1, 2, 3, 4, 5 microg litre(-1)) or received short-term (10-h) exposure to 5 microg carbaryl litre(-1) at different life stages of the animal. In the long-term exposure experiments carbaryl at 1 microg litre(-1) did not have any detectable effects on the animals, whereas 2 microg litre(-1) reduced the survival, growth and reproduction of the animals, and higher concentrations killed all the animals examined before they grew to the fifth instar. These results indicate that the range of sublethal concentrations of carbaryl for D. ambigua is narrow. In the short-term exposure experiments the animals did not suffer any damage when they were exposed to the chemical during the egg stage. However, their growth and egg production were reduced when the short-term exposure was conducted during the life stages from the final embryo stage to the third instar. The effect was most marked when the animals were treated during the first instar, indicating that this is the stage when the animals are most sensitive to the chemical.     

Acute and chronic ecotoxicity of carbaryl with a battery of aquatic bioassays

The ecotoxic effects of carbaryl (carbamate insecticide) were investigated with a battery of four aquatic bioassays. The nominal effective concentrations immobilizing 50% of Daphnia magna (EC50) after 24 and 48 h were 12.76 and 7.47 µg L^?1, respectively. After 21 days of exposure of D. magna, LOECs (lowest observed effect concentrations) for cumulative molts and the number of neonates per surviving adult were observed at carbaryl concentration of 0.4 µg L^?1. An increase of embryo deformities (curved or unextended shell spines) was observed at 1.8 and 3.7 µg L^?1, revealing that carbaryl could act as an endocrine disruptor in D. magna. Other bioassays of the tested battery were less sensitive: the IC50-72h and IC10-72h of the algae Pseudokirchneriella subcapitata were 5.96 and 2.87 mg L^?1, respectively. The LC50-6d of the ostracod Heterocypris incongruens was 4.84 mg L^?1. A growth inhibition of H. incongruens was registered after carbaryl exposure and the IC20-6d was 1.29 mg L^?1. Our results suggest that the daphnid test sensitivity was better than other used tests. Moreover, carbaryl has harmful and toxic effects on tested species because it acts at low concentrations on diverse life history traits of species and induce embryo deformities in crustaceans.     

Persistence and biodegradation of carbaryl in soils

Abstract

The persistence of the methylcarbamate pesticide carbaryl was studied in four soils under flooded conditions. A substantial portion of the pesticide was recovered from all soils even after 15 days of its application, with the recovery ranging from 37% in an alluvial soil to 73% in an acid sulfate soil. The degradation of carbaryl was more rapid under flooded conditions than under nonflooded conditions. A bacterium, Pseudomonas cepacia, isolated from a flooded soil amended with a related methylcarbamate pesticide carbofuran, degraded carbaryl in a mineral medium supplemented with yeast extract.     

Effects of bacterial counts and temperature on the biodegradation of bisphenol A in river water

Total 15 surface river waters were collected from thirteen different rivers to investigate a relationship of bacterial counts and temperature to the degradation of bisphenol A (BPA). Autoclaved and non-autoclaved river water samples were spiked with 0.2 mg/l BPA. The spiked samples were placed at temperatures of 4, 20, and 30 degrees C and analyzed by high performance liquid chromatography. BPA was degraded at all temperatures in the non-autoclaved samples. However, BPA in the autoclaved samples was not changed at all temperatures for 20 d. These results show that the primary factor of BPA degradation in river water is bacteria. Moreover, three groups [group A (> 10000 CFU/ml), group B (2000-10000 CFU/ml), and group C (< 2000 CFU/ml)], were made on the basis of bacterial counts of the samples. Half-lives for BPA degradation in groups A, B, and C were 2, 3, and 6 d at 30 degrees C and were 4, 5, and 7 d at 20 degrees C, respectively. But at 4 degrees C, the loss of BPA was about 40%, 20%, and 10% in groups A, B, and C for 20 d, respectively. Bacterial counts exerted an influence on BPA degradation in river water with temperature. Our results also show that BPA-degrading bacteria are widely distributed in river waters.     

An integrated approach for assessing the migration behavior of chlorpyrifos and carbaryl in the unsaturated soil zone

Chlorpyrifos (O, O-diethyl O-3,5,6-trichloropyridin-2-yl phosphorothioate) and carbaryl (1-naphthyl methylcarbamate) are often applied concurrently as insecticides in food production. The aim of this study was to research their migration behavior in a real environment. We researched the leaching of both pesticides by setting up field lysimeters on a farm with the typical soil used in fruit production today. In order to analyze the variables involved in this process, we performed complementary adsorption studies, we performed complementary adsorption studies using batches and undisturbed soil laboratory columns for both compounds. The results for pesticide transport through the lysimeters showed that less than 1% of chlorpyrifos was recovered in the leachates, while almost 17% was recovered for carbaryl. Having completed the experiment in undisturbed laboratory columns, soil analysis showed that chlorpyrifos mainly remained in the first 5 cm, while carbaryl moved down to the lower sections. These results can be explained in view of the sorption coefficient values (K_D) obtained in horizons A and B for chlorpyrifos (393 and 184 L kg^?1) and carbaryl (3.1 and 4.2 L kg^?1), respectively. By integrating the results obtained in the different approaches, we were able to characterize the percolation modes of these pesticides in the soil matrix, thus contributing to the sustainable use of resources.     

Determination of pesticide residues in IPM and non-IPM samples of mango (Mangifera indica)

Studies were conducted to analyze the residue of commonly used pesticides viz. methyl parathion, chloropyrifos, endosulfan, cypermethrin, fenvalerate, carbendazim, imidacloprid and carbaryl in mango, Dashehari variety, integrated pest management (IPM) and non-IPM samples were collected from the IPM and non-IPM orchards, Lucknow, India. We also present a method for the simultaneous determination of these pesticides in mango samples. Residues of methyl parathion, chloropyriphos, endosulfan, cypermethrin, fenvalerate were extracted from the samples with acetone: cyclohexane: ethyl acetate in the ratio 2:1:1 followed by cleanup using neutral alumina. Analysis was performed by gas chromatography-electron capture detector (GC-ECD) with a megabore column (OV-1). Residues of carbendazim, imidacloprid and carbaryl were extracted with acetone and after cleanup, analysis was performed by high performance liquid chromatography (HPLC) using photo diode array (PDA) detector. Recoveries of all the pesticides ranged between 72.7-110.6%, at 0.1 and 1.0 microg g(-1) level of fortification. The residues detected in non-IPM samples of mango were found to be below the prescribed limits of maximum residue limit (MRL) while IPM samples were free from pesticide residues.     

Acetochlor mineralization and fate of its two major metabolites in two soils under laboratory conditions

The degradation of the herbicide acetochlor, in a neoluvisol and in a calcosol were studied as a function of depth (0-25cm and 25-50cm) and temperature (25 degrees C and 15 degrees C) under controlled laboratory conditions during 58 and 90 days, respectively. The surface and sub-surface soil samples were respectively spiked with 1 and 0.01mgkg(-1) of 14C-acetochlor, the concentrations observed in previous field monitoring. The half-lives (DT50) varied from 1.4 to 14.9 days depending on the soil, temperature and applied concentration. The maximal mineralization (24%) was observed for the surface calcosol at 25 degrees C. The comparison of results obtained for sterilized and non-sterilized soils, the decrease of DT50 with the increase of temperature, the shape of CO2 emissions and the increase of number of aerobic endogenous microflora through the experiment suggested that biological process are dominant in degradation. A particular attention was paid to the formation and dissipation of metabolites ESA (ethanesulphonic acid) and OA (oxanilic acid) during the whole experiment. At 25 degrees C, ESA and OA were observed after three days, but as ESA concentration decreased over time in surface calcosol, it remained constant in surface neoluvisol. A difference in ESA/OA ratio depends on the soil with a predominance of OA in surface neoluvisol and a disappearance of OA in surface calcosol.     

微乳液法合成掺硫纳米TiO_2及其光催化性能研究

以钛酸四丁酯为钛源,硫脲为掺硫前驱物,采用聚乙二醇辛基苯基醚（Triton X-100）/正己醇/环己烷/氨水的微乳液体系合成了掺硫的纳米TiO2粉体;对其结构进行了表征,以甲基橙为目标降解物考察了其光催化性能。烧结温度通过影响TiO2的晶型转变和颗粒尺寸来影响其光催化性能,随着烧结温度的升高,TiO2的光催化性能先是提高,然后迅速降低;在600℃烧结2 h时催化剂的降解性能达到最佳。掺杂硫可提高TiO2的光催化活性,随着掺杂量的增加,催化剂对甲基橙的降解率先快速增加然后缓慢降低,当掺杂量为S/Ti（摩尔比）=0.01∶1时TiO2的光催化降解效果最好。催化剂在用量较小时迅速提高TiO2的光催化降解性能,而后随着用量的增大反而降低,当催化剂用量为1.5 g/L时,对甲基橙的降解效果最好。     

Determination of pesticide residues in IPM and non-IPM samples of mango (Mangifera indica)

Studies were conducted to analyze the residue of commonly used pesticides viz. methyl parathion, chloropyrifos, endosulfan, cypermethrin, fenvalerate, carbendazim, imidacloprid and carbaryl in mango, Dashehari variety, integrated pest management (IPM) and non-IPM samples were collected from the IPM and non-IPM orchards, Lucknow, India. We also present a method for the simultaneous determination of these pesticides in mango samples. Residues of methyl parathion, chloropyriphos, endosulfan, cypermethrin, fenvalerate were extracted from the samples with acetone: cyclohexane: ethyl acetate in the ratio 2:1:1 followed by cleanup using neutral alumina. Analysis was performed by gas chromatography-electron capture detector (GC-ECD) with a megabore column (OV-1). Residues of carbendazim, imidacloprid and carbaryl were extracted with acetone and after cleanup, analysis was performed by high performance liquid chromatography (HPLC) using photo diode array (PDA) detector. Recoveries of all the pesticides ranged between 72.7 – 110.6%, at 0.1 and 1.0 μg g^{? 1} level of fortification. The residues detected in non-IPM samples of mango were found to be below the prescribed limits of maximum residue limit (MRL) while IPM samples were free from pesticide residues.     

Remediation of 4-nonylphenol in aqueous solution by using free radicals generated by the oxidative reactions

Introduction

This study relates to use of zerovalent iron to generate hydroxyl free radicals and undergo subsequent oxidation to destroy 4-nonylphenol (NP) by mild process in aqueous solution and activation of oxygen gas (O₂) at room temperature. This technology is based on a novel oxidative mechanism mediated by zerovalent iron rather than commonly used reduction mechanism.

Materials and methods

A laboratory scale device consisting of a 250?ml pyrex serum vials fixed to a Vortex agitator was used. Different amounts of zerovalent iron powder (ZVI; 1, 10, and 30?g/l) at pH?4 and room temperature with bubbling of oxygen gas were investigated.

Results and conclusion

Experiments showed an observed degradation rate k _(obs) directly proportional to the amount of iron. 4-Nonylphenol degradation reactions demonstrated first-order kinetics with a half-life of about 10.5?±?0.5 and 3.5?±?0.2?min when experiments were conducted at [ZVI]?=?1 and 30?g/l respectively. Three analytical techniques were employed to monitor 4-nonylphenol degradation and mineralization: (1) spectrofluorimetry; (2) high-performance liquid chromatography; (3) total organic carbon meter (TOC meter). Results showed a complete disappearance of 4-nonylphenol after 20?min of contact with ZVI. The intermediate by-products of the reaction were not identified but the disappearance of NP was monitored by the three above-mentioned techniques.     

Tropical surface water quality studies: Implications for the aquatic fate of N-methyl carbamate pesticides

Water quality assessment was conducted on the Ruiru River, a tributary of an important tropical river system in Kenya, to determine baseline river conditions for studies on the aquatic fate of N-methyl carbamate (NMC) pesticides. Measurements were taken at the end of the long rainy season in early June 2013. Concentrations of copper (0.21–1.51 ppm), nitrates (2.28–4.89 ppm) and phosphates (0.01–0.50 ppm) were detected at higher values than in uncontaminated waters, and attributed to surface runoff from agricultural activity in the surrounding area. Concentrations of dissolved oxygen (8–10 ppm), ammonia (0.02–0.22 ppm) and phenols (0.19–0.83 ppm) were found to lie within normal ranges. The Ruiru River was found to be slightly basic (pH 7.08–7.70) with a temperature of 17.8–21.2°C. The half-life values for hydrolysis of three NMC pesticides (carbofuran, carbaryl and propoxur) used in the area were measured under laboratory conditions, revealing that rates of decay were influenced by the electronic nature of the NMCs. The hydrolysis half-lives at pH 9 and 18°C decreased in the order carbofuran (57.8 h) > propoxur (38.5 h) > carbaryl (19.3 h). In general, a decrease in the electron density of the NMC aromatic ring increases the acidity of the N-bound proton removed in the rate-limiting step of the hydrolysis mechanism. Our results are consistent with this prediction, and the most electron-poor NMC (carbaryl) hydrolyzed fastest, while the most electron-rich NMC (carbofuran) hydrolyzed slowest. Results from this study should provide baseline data for future studies on NMC pesticide chemical fate in the Ruiru River and similar tropical water systems.     

Novel pipette-tip graphene/poly (vinyl alcohol) cryogel composite extractor for the analysis of carbofuran and carbaryl in water

A novel pipette-tip extractor of a graphene/poly (vinyl alcohol) cryogel (graphene/PVA) composite sorbent was prepared to preconcentrate carbamate pesticides in environmental water samples before analysis with a gas chromatograph-flame ionization detector (GC-FID). This novel pipette-tip extractor with the graphene/PVA sorbent exhibited a high porosity when observed through a scanning electron micrograph (SEM). Under optimal conditions, using only 1.0 mL of sample and 0.75 mL of eluting solvent, the developed method provided a wide linear range of 10–700 ng mL^?1 and 10–500 ng mL^?1 with limit of detection (LOD) of 6.40 ± 0.18 and 9.17 ± 0.34 ng mL^?1 for carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) and carbaryl (1-naphthyl methylcarbamate), respectively. The pipette-tip extractor provided high extraction efficiency with high accuracy indicated, by good recoveries in the range of 74.5 ± 4.8% to 119.7 ± 1.6% and 76 ± 15% to 114 ± 19% for carbofuran and carbaryl, respectively. In addition, the fabrication procedure showed a good pipette-tip extractor-to-pipette-tip extractor reproducibility with a relative standard deviation of 1.3–9.8% (n = 5). When the developed pipette-tip extractor was applied for the extraction of carbofuran and carbaryl in surface water samples near vegetable plantation areas, 25.9 ± 8.2 ng mL^?1 of carbofuran was found, and carbaryl was also detected in concentrations that ranged from 45.0 ± 4.0 to 191 ± 13 ng mL^?1.