An effective configuration for automated magnetic micro solid-phase extraction of phenylurea herbicides from water samples followed by high-performance liquid chromatography.

In this study, a new automated magnetic micro solid-phase extraction was introduced. A Tygon tube was folded and fixed around the pole of a cylindrical magnet. Nanosized magnetic sorbents modified with diphenyldichlorosilane were uniformly immobilized on one side of the inner wall of the tube. Sample solution and desorption solvent were passed through the tube using a peristaltic pump. Four phenylurea herbicides (tebuthiuron, monolinuron, isoproturon, and monuron) were used as the model compounds to evaluate the method performance. HPLC-UV was used to separate and quantify the analytes. The effective parameters influencing the performance of the extraction process (i.e., extraction and desorption flow rates, eluent and sample volumes, type of eluent and sample ionic strength) were investigated. The limit of detection was 0.04 µg L-1 for all studied compounds. Calibration curves were linear in the range of 0.1-500 µg L-1 with a determination coefficient between 0.9988 and 0.9999. Intra-day, inter-day and batch-to-batch precisions expressed as relative standard deviation were less than 7%. Several environmental water samples were investigated to assess the applicability of the method for real sample analysis.

Sorption of carbendazim and linuron from aqueous solutions with activated carbon produced from spent coffee grounds: Equilibrium, kinetic and thermodynamic approach.

Spent coffee grounds (SCG) have been used for the production of activated carbon (AC) by impregnation with different ratios of phosphoric acid at 600 °C, Xp (H3PO4/coffee): 3:130%, 4:130%, 3:150% and 4:150%. The obtained AC was characterized by BET, FTIR and SEM. BET surface area corresponds to 803.422 m2 g-1. The influences of the main parameters such as contact time, the pesticides initial concentration, adsorbent dose, pH and temperature on the efficiency of separation process were investigated during the batch operational mode. Results were modeled by adsorption isotherms: Langmuir, Freundlich and Temkin isotherms, which gave satisfactory correlation coefficients. The maximum adsorption capacities calculated from the Langmuir isotherms were 11.918 mg g-1 for carbendazim and 5.834 mg g-1 for linuron at room temperature. Adsorption kinetics of carbendazim and linuron have been studied by the pseudo-first-order, the pseudo-second-order and the intraparticle diffusion model. The results of adsorption kinetics have been fitted the best by pseudo-second-order model. The resulted data from FTIR characterization pointed to the presence of many functional groups on the AC surface. SCG adsorbent, as an eco-friendly and low-cost material, showed high potential for the removal of carbendazim and linuron from aqueous solutions.

Minimal pesticide-primed soil inoculum density to secure maximum pesticide degradation efficiency in on-farm biopurification systems.

Addition of pesticide-primed soil containing adapted pesticide degrading bacteria to the biofilter matrix of on farm biopurification systems (BPS) which treat pesticide contaminated wastewater, has been recommended, in order to ensure rapid establishment of a pesticide degrading microbial community in BPS. However, uncertainties exist about the minimal soil inoculum density needed for successful bioaugmentation of BPS. Therefore, in this study, BPS microcosm experiments were initiated with different linuron primed soil inoculum densities ranging from 0.5 to 50 vol.% and the evolution of the linuron mineralization capacity in the microcosms was monitored during feeding with linuron. Successful establishment of a linuron mineralization community in the BPS microcosms was achieved with all inoculum densities including the 0.5 vol.% density with only minor differences in the time needed to acquire maximum degradation capacity. Moreover, once established, the robustness of the linuron degrading microbial community towards expected stress situations proved to be independent of the initial inoculum density. This study shows that pesticide-primed soil inoculum densities as low as 0.5 vol.% can be used for bioaugmentation of a BPS matrix and further supports the use of BPS for treatment of pesticide-contaminated wastewater at farmyards.

Sonochemical and sonocatalytic degradation of monolinuron in water.

The degradation of the phenylurea monolinuron (MLN) by ultrasound irradiation alone and in the presence of TiO(2) was investigated in aqueous solution. The experiments were carried out at low and high frequency (20 and 800 kHz) in complete darkness. The degradation of MLN by ultrasounds occurred mainly by a radical pathway, as shown the inhibitory effect of adding tert-butanol and bicarbonate ions to scavenge hydroxyl radicals. However, CO(3)(-) radicals were formed with bicarbonate and reacted in turn with MLN. In this study, the degradation rate of MLN and the rate constant of H(2)O(2) formation were used to evaluate the oxidative sonochemical efficiency. It was shown that ultrasound efficiency was improved in the presence of nanoparticles of TiO(2) and SiO(2) only at 20 kHz. These particles provide nucleation sites for cavitation bubbles at their surface, leading to an increase in the number of bubbles when the liquid is irradiated by ultrasound, thereby enhancing sonochemical reaction yield. In the case of TiO(2), sonochemical efficiency was found to be greater than with SiO(2) for the same mass introduced. In addition to the increase in the number of cavitation bubbles, activated species may be formed at the TiO(2) surface that promote the formation of H(2)O(2) and the decomposition of MLN.

Mineralisation of the herbicide linuron by Variovorax sp. strain RA8 isolated from Japanese river sediment using an ecosystem model (microcosm).

BACKGROUND: Linuron is a globally used phenylurea herbicide, and a large number of studies have been made on the microbial degradation of the herbicide. However, to date, the few bacteria able individually to mineralise linuron have been isolated only from European agricultural soils. An attempt was made to isolate linuron-mineralising bacteria from Japanese river sediment using a uniquely designed river ecosystem model (microcosm) treated with (14)C-ring-labelled linuron (approximately 1 mg L(-1)). RESULTS: A linuron-mineralising bacterium that inhabits river sediment was successfully isolated. The isolate belongs to the genera Variovorax and was designated as strain RA8. Strain RA8 gradually used linuron in basal salt medium (5.2 mg L(-1)) with slight growth. In 15 days, approximately 25% of (14)C-linuron was mineralised to (14)CO(2), with 3,4-dichloroaniline as an intermediate. Conversely, in 100-fold diluted R2A broth, strain RA8 rapidly mineralised (14)C-linuron (5.5 mg L(-1)) and more than 70% of the applied radioactivity was released as (14)CO(2) within 3 days, and a trace amount of 3,4-dichloroaniline was detected. Additionally, the isolate also degraded monolinuron, metobromuron and chlorobromuron, but not diuron, monuron or isoproturon. CONCLUSION: Although strain RA8 can grow on linuron, some elements in the R2A broth seemed significantly to stimulate its growth and ability to degrade. The isolate strictly recognised the structural difference between N-methoxy-N-methyl and N,N-dimethyl substitution of various phenylurea herbicides.

Coupled solar photo-Fenton and biological treatment for the degradation of diuron and linuron herbicides at pilot scale.

A coupled solar photo-Fenton (chemical) and biological treatment has been used to remove biorecalcitrant diuron (42 mg l(-1)) and linuron (75 mg l(-1)) herbicides from water at pilot plant scale. The chemical process has been carried out in a 82 l solar pilot plant made up by four compound parabolic collector units, and it was followed by a biological treatment performed in a 40 l sequencing batch reactor. Two Fe(II) doses (2 and 5 mg l(-1)) and sequential additions of H2O2 (20 mg l(-1)) have been used to chemically degrade the initially polluted effluent. Next, biodegradability at different oxidation states has been assessed by means of BOD/COD ratio. A reagent dose of Fe=5 mg l(-1) and H2O2=100 mg l(-1) has been required to obtain a biodegradable effluent after 100 min of irradiation time. Finally, the organic content of the photo-treated solution has been completely assimilated by a biomass consortium in the sequencing batch reactor using a total suspended solids concentration of 0.2 g l(-1) and a hydraulic retention time of 24h. Comparison between the data obtained at pilot plant scale (specially the one corresponding to the chemical step) and previously published data from a similar system performing at laboratory scale, has been carried out.

Life cycle assessment of the removal of Diuron and Linuron herbicides from water using three environmentally friendly technologies.

Nowadays, every chemical treatment must be developed taking into account its global impact on the environment. With this objective a life cycle assessment (LCA) has been used as a tool for the assessment of the environmental impact of three environmentally friendly processes for the removal of Diuron and Linuron herbicides from water: artificial light assisted photo-Fenton, photo-Fenton coupled to biological treatment and solar assisted photo-Fenton. The inventoried data has been classified considering the potential environmental impacts categories included in the CML 2 baseline 2000 method. Among the three scenarios considered, photo-Fenton coupled to biological treatment proved to have the lowest environmental impact in all the studied categories due to the lower hydrogen peroxide and electricity consumptions. The environmental impacts associated with hydrogen peroxide and electricity production imply more than 72% in all the impact categories of the three scenarios, except for aquatic eutrophication potential category, where the main impacts are related to nitrogen emissions.