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.

Methemoglobinemia Following Monolinuron Ingestion: A Case Report in a Child.

CASE: We describe a case report of a 2-year-old boy presenting to the emergency department with cyanosis and agitation. There was no suggestive history of poisoning but parents reported the presence of an aquarium at the family dinner the night before, with an aquarium cleaner beside it. Physical examination at admission revealed central cyanosis without signs of respiratory distress. Oxygen saturation measured by pulse oximetry (SpO2) was at 80% in room air. Plasma level of methemoglobin was measured at 11.8%. After 6 hours, methemoglobin decreased spontaneously to 5% and pulse oximetry saturation reached 98% in room air. Consciousness, weakness, and behavior were concomitantly improved. Because of rapid and spontaneous improvement, no specific treatment such as methylene blue was administered. A mass spectrometry toxicological analysis was performed in a blood sample taken the day of admission. Screening procedure of pesticides based on liquid chromatography coupled with mass spectrometry identified monolinuron, a phenylurea herbicide. CONCLUSIONS: We recommend considering acquired methemoglobinemia after ingestion of industrial products and drugs in children with cyanosis, mental status alteration, and without respiratory distress symptoms.

Assessing single and joint toxicity of three phenylurea herbicides using Lemna minor and Vibrio fischeri bioassays.

Single and joint toxicity of three substituted urea herbicides, namely monolinuron [3-(4-chlorophenyl)-1-methoxy-1-methylurea], linuron [3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea] and diuron [1-(3,4 dichlorophenyl)-3,3 dimethyl urea], were studied. The duckweed Lemna minor and the luminescent bacterium Vibrio fischeri were used for the toxicity assessment and they were exposed to various concentrations of the herbicides, individually and in binary mixtures. The exposure time was 7d for the duckweed and 30 min for the bacterium. Estimation of EC50 values was performed by frond counting and reduction in light output for Lemna minor and Vibrio fischeri, respectively. Lemna minor was found to be much more sensitive than Vibrio fischeri to target compounds. The toxicity of the three herbicides applied solely was estimated to be in decreasing order: diuron (EC50=28.3 µg L(-1))≈linuron (EC50=30.5 µg L(-1))>monolinuron (EC50=300 µg L(-1)) for the duckweed and linuron (EC50=8.2 mg L(-1))>diuron (EC50=9.2 mg L(-1))>monolinuron (EC50=11.2 mg L(-1)) for the bacterium. Based on the environmental concentrations reported in the literature and EC50 values obtained from Lemna minor experiments, Risk Quotients (RQ) much higher than 1 were calculated for diuron and linuron. In Lemna minor experiments, combination of target compounds resulted to additive effects due to their same mode of phenylurea action on photosynthetic organisms. Regarding Vibrio fischeri, synergistic, additive and antagonistic effects were observed, which varied according to the concentrations of target compounds.

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.

Investigation of photodegradation and hydrolysis of selected substituted urea and organophosphate pesticides in water.

INTRODUCTION: Photodegradation and hydrolysis of two substituted urea herbicides, monolinuron [3-(4-chlorophenyl)-1-methoxy-1-methylurea] and linuron [3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea], and one organophosphorous insecticide, phoxim [2-(diethoxyphosphinothioyloxyimino)-2-phenylacetonitrile], were studied using buffered sterilized distilled water (pH 4, 7 and 9). METHODS: Experiments were performed in the absence and presence of light (320-740 nm), while the effect of nitrates and humic acids on photodegradation was investigated for all pH values. An analytical method was developed and validated for the determination of target compounds in water samples using liquid chromatography positive ion electrospray-mass spectrometry. RESULTS: According to the results, substituted ureas neither hydrolyzed, at all tested pH values, nor photodegraded at pH 7 and 9. Slow photodegradation of the compounds was observed at pH 4. During 70 days of light exposure, initial concentrations of linuron and monolinuron were decreased by 54% and 31%, respectively, while the presence of nitrates slightly enhanced photodegradation of these compounds. On the other hand, phoxim was found to be very unstable for all the tested conditions and an increase of pH resulted to higher degradation. During hydrolysis experiments, the degradation of the compound ranged from 41% (pH 4) to 85% (pH 9) and the half-lives varied from 10 h (pH 9) to 204 h (pH 4). The presence of light enhanced phoxim degradation and as a result half-lives of 37, 22 and 9h were calculated for pH 4, 7 and 9, respectively. The addition of nitrates and humic acids did not significantly affect the photodegradation of phoxim. CONCLUSIONS: The results indicated that among the three tested pesticides, phoxim found to be the most sensitive in both photodegradation and hydrolysis.

Determination of phenylurea herbicides in aqueous samples using partitioned dispersive liquid-liquid microextraction.

Partitioned dispersive liquid-liquid microextraction (PDLLME), using THF as the dispersive solvent and dichloromethane as the extraction solvent, was utilized to isolate and concentrate phenylurea herbicides (PUHs) from aqueous samples. In PDLLME, a dispersive solvent should be able to partition in the organic extractant droplets to effectively extract the polar organic compounds from aqueous samples. The mixture of the water-immiscible extractant and the partitioned dispersive solvent was obtained by centrifugation, dried under low pressure, reconstituted in methanol-water mixture (1:1), and injected into a HPLC system for the determination of PUHs. The enrichment factors of the PUHs ranged from 68 to 126 under the optimal conditions. The linear range was 0.5-100 ng ml(-1) for each analyte, the relative standard deviations of PUHs were in the range of 1.5-5.9% (n=5), and the detection limits (signal-to-noise ratio of 3) ranged from 0.10 to 0.28 ng ml(-1) for the herbicides. The range of intraday precision (n=5) for PUHs at the levels of 0.5, 5, and 50 ng ml(-1) were 3.0-5.9%, 1.8-3.3%, and 2.2-3.6%, respectively. The range of interday precision (n=5) at 0.5, 5, and 50 ng ml(-1) were 0.4-1.8%, 1.2-2.4%, and 0.9-2.3%, respectively. The recoveries of PUHs from three spiked river water samples, at a level of 10 ng ml(-1), were 91.2-104.1%. Due to its rapidity, ease of operation, and high recovery, PDLLME can be utilized to isolate and concentrate organic environmental contaminants such as PUHs from aqueous samples.

Direct determination of monolinuron, linuron and chlorbromuron residues in potato samples by gas chromatography with nitrogen-phosphorus detection.

A gas chromatography with nitrogen-phosphorus detection direct method for methoxyurea herbicide determination in powdered potato and fresh potato samples has been developed. A previous study of the thermal stability of the phenylurea herbicides seems to confirm that the ones containing the methoxy radical, i.e. monolinuron, linuron and chlorbromuron, were stable. The herbicides were extracted from the sample through liquid-liquid extraction with dichloromethane-light petroleum (1:1), followed by solid-phase extraction in a C8 cartridge. The recoveries were in the range 84-95% for powdered potato and 86-101% for fresh potato. The RSD values were less than 10%, at 0.1 microg g(-1) concentration level (n = 4) for both types of samples. Detection limits of the method were 7.0-30 ng g(-1) for powdered potato and 6.0-50 ng g(-1) for fresh potato.

Determination of traces of pesticides in water by solid-phase extraction and liquid chromatography-ionspray mass spectrometry.

A multi-residue analytical method for six pesticides (atrazine, hydroxyatrazine, carbofuran, promecarb, linuron and monolinuron) in drinking water has been developed. The method combines liquid chromatography and mass spectrometry using an ionspray interface. The linearity domain, as well as the limits of detection and quantification, were determined for each compound. Although satisfactory performance could be achieved, present drinking water regulations (0.1 microgram l-1 for single pesticide) requires a pre-concentration step. This was performed using solid-phase extraction with octadecyl-bonded silica cartridges. The analytical procedure was tested on water samples spiked at the 0.04 and 0.08 microgram l-1 levels, and allowed the determination of the investigated pesticides (except hydroxyatrazine) at these trace concentrations.

The effect of p-chloroaniline on leucocytes of sheep peripheral blood under the migration-inhibition test conditions.

Toxic and immunotoxic effects of p-chloroaniline--a metabolite of herbicide monolinuron--were investigated in peripheral blood leucocytic suspensions of five sheep using a migration-inhibition test. The toxic effect of p-chloroaniline was recorded at concentrations 1.0 to 0.1 mg.ml-1 and the immunotoxic one at concentrations 0.01-0.001 mg.l-1. The toxic effect was demonstrated by total inhibition of leucocyte migration. The immunotoxic effect, determined as mitogenic activation of leucocytes by phytohemagglutinin, concanavalin A and lipopolysaccharide, was detected at 10 to 100-fold lower concentrations of p-chloroaniline than those which resulted in toxic effects.

Methemoglobinemia following ingestion of a monolinuron/paraquat herbicide (Gramonol)

A 59-year-old man ingested a mouthful of Gramonol with suicidal intent and was admitted to a local hospital six and a half hours later. It was noted that he looked "ashen grey" and was centrally cyanosed. The methemoglobin and plasma paraquat concentrations performed on arrival at the Regional Poisons Treatment Unit eight hours after paraquat ingestion were 52% and 1100 micrograms/L respectively; the administration of methylene blue reversed methemoglobinemia within two hours. The patient suffered extensive paraquat-induced oral, and probably esophageal, ulceration and developed multiple organ (particularly renal, respiratory and hepatic) failure and died some 10 days later. This is the most severe case of Gramonol poisoning reported both in terms of the amount of paraquat ingested and the concentration of methemoglobin formed. We believe that the methemoglobinemia in this patient was caused by monolinuron not paraquat.

Fate of [14C]monolinuron in potatoes and soil under outdoor conditions.

[phenyl-14C]Monolinuron was applied (2.5 and 1.9 kg/ha) to the soil surface of an outdoor lysimeter in two successive years: then, potatoes were grown. Total recovery of 14C in soil, plants, and leached water was about 55% (of 14C applied) after the first growing period and about 43% after the second growing period. Radioactivity in soil contained 77.1% (based on total 14C recovered in soil) bound residues, 15% monolinuron, and the following conversion products: N-(4-hydroxyphenyl)-N'-methoxy-N'-methylurea, N-(4-chlorophenyl)-N'-methylurea. N-(4-chlorophenyl)methylcarbamate, N-(4-chlorophenyl)-N-methyl-methylcarbamate, and 4-chloroformanilide. The leachate contained 0.8% (based on total 14C recovered in leachate) N-(4-hydroxyphenyl)-N'-methoxy-N'-methylurea. Potato plants contained 0.106 mg/kg radioactive residues in peeled tubers after one growing period and 15.94 mg/kg in the tops; after two growing periods, peeled tubers contained 0.091 mg/kg and tops contained 18.87 mg/kg radioactive residues. These residues consisted of bound 14C (57.9% of total 14C recovered in plants), N-(4-hydroxyphenyl)-N'-methoxy-N'-methylurea, N-(4-chlorophenyl)-N'-methylurea, N-(4-chlorophenyl)methylcarbamate, N-(4-chlorophenyl)-N-methyl-methylcarbamate, and 4,4'-dichlorozobenzene.

A comparative study on pesticide formulations for application in running waters.

Release rates into water of monolinuron, desmetryne, and carbofuran from three different types of formulations have been studied to control aquatic weeds in running waters. The migration of active ingredients (AI) from conventional wettable powder formulations was complete within 1 day, while the migration from ethylene-vinyl acetate copolymeric matrix (EVA) lasted significantly longer due to low diffusion coefficients of monomeric pesticides in polymeric matrices Do = 10(-8)-10(-12) (cm2 X sec-1). The herbicidal action could be extrapolated up to several years. Release duration of AI from calcium alginate beads lasted 2 weeks. Herbicidal effectiveness of terbutryne-EVA formulation has been investigated in a laboratory-scale simulated flow system device with duckweed plants (Lemna minor) as test organism. Growth inhibition of duckweed could be achieved at approx 20 ppb terbutryne in steady state.

[Biotransformation of monolinuron (N-(4-chlorophenyl)-N'-methyl-N'methoxyurea) in isolated perfused chicken liver]. / Biotransformation von Monolinuron (N-(4-Chlorphenyl)-N'-methyl-N'-methoxyharnstoff) in der isoliert perfundierten Hühnerleber.

The biotransformation of radioactively labelled monolinuron (N-(4-chloro[U-14C]phenyl)-N'-methyl-N'-methoxyurea) was studied in the isolated perfused liver of the chicken. After a 4-hr perfusion, 83.1% of the added radioactivity was recovered, 56.6% in the perfusion medium and 26.5% in the liver and bile. The fraction of radioactivity extractable from the perfusion medium into ethyl acetate amounted to 47.8% of the added dose. In addition to monolinuron, five breakdown products were identified in this extract, namely N-(4-chlorophenyl)-N'-hydroxymethyl-N'-methoxyurea, N-(4-chlorophenyl)-N'-methoxyurea, N-(4-chlorophenyl)-N'-methylurea, 4-chlorophenylurea and 4-chloroacetanilide. Of particular interest was the absence of arylhydroxylated monolinuron derivatives, since in monolinuron-metabolism studies in the laying hen 2-hydroxy-4-chlorophenylurea and 3-hydroxy-4-chlorophenylurea were both detected. This differing metabolism corresponds to earlier findings in the rat, in which arylhydroxylated breakdown products were detected only in in vivo studies and not in rat-liver perfusion. Possible reasons for the differing metabolism of monolinuron in vivo and in vitro are discussed.