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Comparative toxic effects of formulated simazine on Vibrio fischeri and gilthead seabream (Sparus aurata L.) larvae.

The use of Early Life Stage (ELS) tests is a useful tool in risk assessment. The purpose of this study was to compare the sensitivity of the seabream (Sparus aurata) larvae with the extensively used Microtox test on a commercial formulation containing simazine, an s-triazine herbicide. To this end, survival, growth and histopathological changes displayed by seabream yolk sac larvae exposed during 72 h post-hatching to nominal concentrations of the commercial preparation up to its saturating concentration in water, and bioluminescence of the marine bacteria Vibrio fischeri (Microtox) were studied. Survival of larvae after three days of exposure was significantly reduced in the highest (4.5 mg/l) concentration, but no effects on growth were found in any of the simazine treatments. The 72 h LC50 value for yolk sac larvae was estimated as 4.19 mg/l. Commercial grade simazine did not exert any significant toxicity to the marine bacterium V. fischeri at the concentrations tested.

Aliivibrio fischeri↗

Rapid determination of simazine and atrazine in water at the parts per trillion (10(12) level. Extraction by a miniaturized carbopack B trap followed by high-performance liquid chromatography.

A rapid and simple method for the determination of trace amounts of simazine and atrazine in water is described. A 250-ml volume of water is pre-concentrated by passage at a flow-rate of about 30 ml/min through a small trap containing 50 mg of graphitized carbon black (Carbopack B). After washing with 150 microliters of methanol, the two herbicides are desorbed with 700 microliters of dichloromethane-methanol (60:40, v/v). After removal, of the solvent, the extracted sample is fractionated and analysed by reversed-phase high-performance liquid chromatography with UV detection at 220 nm. A single assay can be completed within 40 min from the receipt of the water sample. Recoveries of simazine and atrazine added to 250 ml of water at the level of 50 ng/l were 97.2 and 95.8% and the limits of detection were 0.07 and 0.15 ng. respectively. At the 50 ng/l level in water, the coefficients of variation for simazine and atrazine were 3.7 and 4.0% (n = 7), respectively.

Atrazine↗

Sister chromatid exchanges and micronuclei analysis in lymphocytes of men exposed to simazine through drinking water.

In some cities of the autonomous community of Extremadura (south-west of Spain), levels of simazine from 10 to 30 ppm were detected in tap water. To analyse the possible effect of this herbicide, two biomarkers, sister chromatid exchanges (SCE) and micronuclei (MN), were used in peripheral blood lymphocytes from males exposed to simazine through drinking water. SCE and MN analysis failed to detect any statistically significant increase in the people exposed to simazine when compared with the controls. With respect to high frequency cells (HFC), a statistically significant difference was detected between exposed and control groups.

Administration, Oral↗

Direct aqueous injection liquid chromatography/electrospray ionization-mass spectrometry/mass spectrometry analysis of water for atrazine, simazine, and their chlorotriazine metabolites.

A method is reported for the determination of atrazine, simazine, and their respective dealkylated chlorotriazine metabolites in ground, surface, and finished drinking water. Water samples are diluted 1:4 in an injection vial prior to analysis using liquid chromatography/electrospray ionization-mass spectrometry/mass spectrometry (LC/ESI-MS/MS). The lower limit of method validation is 0.10 microg/L (ppb) for 2-chloro-4-(ethylamino)-6-isopropylamino)-s-triazine (atrazine, G-30027), 2-chloro-4, 6-(diethylamino)-s-triazine (simazine, G-27692), 2-amino-4-chloro-6-(isopropylamino)-s-triazine (deethylatrazine, DEA, or G-30033), 2-amino-4-chloro-6-(ethylamino)-s-triazine (deisopropylatrazine, DIA, or G-28279), and 2,4-diamino-6-chloro-s-triazine (didealkylatrazine, DDA, or G-28273). The overall mean procedural recoveries (and % relative standard deviations) for atrazine, simazine, DEA, DIA, and DDA are 98 (4.4), 102 (3.6), 99 (4.8), 103 (4.0), and 109% (4.8%), respectively, in finished drinking water; 108 (2.7), 104 (5.4), 113 (4.5), 111 (5.2), and 105% (5.3%), respectively, in groundwater; and 96 (6.9), 103 (4.2), 102 (4.4), 102 (5.2), and 102% (8.2%), respectively, in surface water. The method validation was conducted under U.S. EPA FIFRA Good Laboratory Practice Guidelines 40 CFR 160.

Atrazine↗

Influence of soil moisture on sorption and degradation of hexazinone and simazine in soil.

Sorption and degradation rates of hexazinone and simazine on soil were determined in a sandy loam soil incubated, during 44 days, at 25 degrees C with moisture contents ranging from 4% to 18%. Herbicide levels in soil solution were also measured, after extraction of this solution by a centrifugation method. All experiments were conducted with treated soil in plastic columns, and the results showed that this method is suitable for the simultaneous study of pesticide sorption and degradation in soil at different environmental conditions. In general, sorption of both herbicides was higher for aged herbicide residues compared to recently applied herbicides, and soil subjected to drying and rewetting cycles had the highest sorption values. K(f) values ranged from 0.5 to 1.2 for simazine and from 0.2 to 0.4 for hexazinone. Degradation rates increased with soil moisture content for both herbicides, and drying-rewetting of soil yielded degradation rates slower than that obtained at 10% soil moisture content. Hexazinone concentration in soil solution decreased with incubation time faster than simazine.

Herbicides↗

Simazine removal from water in a continuous bubble column by O3 and O3/H2O2.

Simazine, [2-chloro, 4,6-bis(ethylamino)-1,3,5-s-triazine], a common herbicide found in surface and ground water has been ozonized in continuous flow mode. Typical operating variables in ozonation processes have been investigated. Thus, the ozone dose fed to the system exerted a positive effect, while the gas flow rate did not influence the efficiency of the process provided ozone mass flow rate was kept constant. Increasing the pH led to a higher extension of the free radical degradation of simazine and, therefore, to a higher efficiency of the process. Also, addition of free radical promoters, i.e. hydrogen peroxide, did result in a significant improvement of the simazine removal rate. A first approach to process economy showed the system ozone/hydrogen peroxide as the most advantageous in terms of electrical energy requirements.

Herbicides↗

The influence of glucose on simazine decomposition.

Glucose added to soil and to the culture medium of Penicillium citrinum stimulated simazine decomposition. Differences in the rate of simazine decomposition depended on the dose of glucose. Both in soil and in the medium the rate of simazine decomposition was connected with the intensity of development of microorganisms.

Chromatography, Thin Layer↗

Simultaneous gas chromatographic determination of carbofuran, metalaxyl, and simazine in soils.

A method for extraction, cleanup, and simultaneous gas chromatographic detection of carbofuran, metalaxyl, and simazine in soils has been developed. Pesticide residues were extracted from soil with acetone containing 10% 0.2M HCl-KCl buffer (pH 2.0), cleaned up with methylene chloride-carbonate buffer (pH 10.7) solvent partitioning and solid-phase extraction on disposable silica gel columns, and quantitated with gas chromatography using a Supelcowax 10 megabore capillary column and a nitrogen-selective detector. Method limits of detection were 0.02 microgram/g for the 3 pesticides in surface soils (0-30 cm depths) and 0.02, 0.02, and 0.005 microgram/g in soils below 30 cm (subsoils) for carbofuran, metalaxyl, and simazine, respectively. Recoveries for carbofuran, metalaxyl, and simazine were 92.6 +/- 5.5, 93.6 +/- 5.0, and 88.4 +/- 6.7%, respectively, when soil samples were spiked with pesticide concentrations ranging from 0.02 to 2.0 micrograms/g.

Alanine↗

[Biological value of Mironovskaya-808 winter wheat grown using the herbicide simazine].

The biological value of spring wheat Mironovskaya-808 grown with the use of simazine which was introduced into soil prior to appearance of shoots at doses of 0.5 and 1.0 kg/ha has been studied. The organoleptic parameters evaluated by the method of closed testing and physicochemical parameters characterizing the corn quality (protein fat, gluten and ash content, moisture, acidity) of experimental samples did not differ from those of the reference sample. Relative biological value of wheat grown with the use of simazine at a dose of 1.0 kg/ha evaluated by the test-object Tetrahymena pyriformis was slightly higher as compared to the control. The effect of test wheat samples on some parameters of protein metabolism was also studied in male rats (the content of protein and its fractions in blood serum, liver and brain as well as activity of enzymes participating in protein metabolism regulation: aminotransferases of blood serum and liver, catepsins, histidase and tryptophan oxygenase of the liver). According to the data obtained no adverse effect of spring wheat Mironovskaya-808 grown with the use of simazine on the above parameters of protein metabolism was recorded in test animals.

Alanine Transaminase↗

[Sister chromatid exchanges induced in human lymphocyte chromosomes by trifluralin, atrazine and simazine].

Many epidemiological and experimental "in vivo" studies have proved in recent years the carcinogenic properties of herbicides. In order to evaluate the "in vitro" action on the human DNA of Trifluralin, Atrazine and Simazine (active principles of herbicides Treflan and Fogard S respectively) the authors have studied the rates of SCE in cultures of human lymphocytes exposed to different concentrations of a solution 1 ppm of the substances. Trifluralin and Simazine, but not Atrazine, increase SCE per cell, with statistical significance, in the cultures with the highest concentrations of these substances. (SCE per cell: Trifluralin 5.27 +/- 1.38, Simazine 5.09 +/- 1.19, Control 3.51 +/- 1.14).

Atrazine↗

Soil dissipation of diuron, chlorotoluron, simazine, propyzamide, and diflufenican herbicides after repeated applications in fruit tree orchards.

In a pear tree orchard planted on loam soil, each plot was treated in April 1998 with either one of the ureas diuron or chlorotoluron, or triazine simazine herbicides applied at 3, 4, and 2 kg AI ha(-1), respectively. Some plots had not been previously treated with one of these herbicides. Other plots had been treated annually during the past 12 years with the same herbicide. One herbicide, and always the same, was thus applied to each plot. In the plots treated for the first time with either diuron, chlorotoluron, or simazine, the soil half-lives of these herbicides in the 0-10 cm surface soil layer were 81, 64, and 59 days, respectively. In the plots treated with the same herbicide for 12 years, the corresponding soil half-lives were 37, 11, and 46 days. Diuron thus produced a moderately enhanced biodegradation, chlorotoluron a high one, and simazine a low but significant one. In another pear tree orchard planted on sandy loam soil, each plot was treated in April 1998 with one of the amide propyzamide (1.25 or 1.0 AI kg ha(-1)) or diflufenican (250 g AI ha(-1)) herbicides. In the plots not previously treated with propyzamide, the propyzamide soil half-life was the same for both doses, i.e., about 30 days. In the plots treated annually for 3 or 14 years with propyzamide, the soil half-life was 12 and 10 days, respectively. In the plots treated for the first time with diflufenican and in those treated annually with diflufenican for 3 years, the diflufenican soil half-life was the same, i.e., 65 days. Propyzamide thus already showed a highly accelerated biodegradation after 3 years of repeated annual applications. Diflufenican, however, did not show enhanced biodegradation after 3 years of repeated annual applications.

Fruit↗

Analysis of trace atrazine and simazine in environmental samples by liquid chromatography-fluorescence detection with pre-column derivatization reaction.

Coupled with off-line extraction, a pre-column derivatization liquid chromatographic fluorescence detection (LC-FL) procedure was developed for the determination of atrazine and simazine in soil, crop and water samples. Concentrations in real samples were expected to be at or below the low ng/g level, which requires pre-concentration of analytes and improved detection. 4-(2-Phthalimidyl) benzoyl chloride (PIB-Cl) was used as a pre-column derivation reagent for high-performance liquid chromatography. The clean-up and second-time concentration procedures, which were indispensable in the conventional analytical methods for soil and crop analysis because of the complexity of the samples, were replaced by a derivatization reaction between PIB-Cl and the analytes. The fluorescent and ultraviolet characteristics of the derivatives were investigated. The derivatization reaction and chromatographic separation conditions were optimized systematically. Detection limits of 1.2 ng/g for atrazine and 1.1 ng/g for simazine were obtained with recoveries of 84-95% for environmental samples. On the basis of practical application to five soil and five crop samples, the LC-FL method was compared with the conventional GC-MS method.

Atrazine↗

Development of an analytical scheme for simazine and 2,4-D in soil and water runoff from ornamental plant nursery plots.

The transport and fate of pesticides applied to ornamental plant nursery crops are not well documented. Methodology for analysis of soil and water runoff samples concomitantly containing the herbicides simazine (1-chloro-4,6-bis(ethylamino)-s-triazine) and 2,4-D ((2,4-dichlorophenoxy)acetic acid) was developed in this research to investigate the potential for runoff and leaching from ornamental nursery plots. Solid-phase extraction was used prior to analysis by gas chromatography and liquid chromatography. Chromatographic results were compared with determination by enzyme-linked immunoassay analysis. The significant analytical contributions of this research include (1) the development of a scheme using chromatographic mode sequencing for the fractionation of simazine and 2,4-D, (2) optimization of the homogeneous derivatization of 2,4-D using the methylating agent boron trifluoride in methanol as an alternative to in situ generation of diazomethane, and (3) the practical application of these techniques to field samples.

2,4-Dichlorophenoxyacetic Acid↗

Mutagenicity of the triazine herbicides atrazine, cyanazine, and simazine in Drosophila melanogaster.

Assays for dominant lethal mutations, sex-linked recessive lethal mutations, and chromosomal breakage, nondisjunction and loss were performed on Drosophila melanogaster males treated by injection or by larval feeding of the herbicides atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine), cyanazine [2-chloro-4-(1-cyano-1-methylethylamino)-6-ethylamino-1,3,5-triazine], or simazine [2-chloro-4,6-bis-(ethylamino)-1,3,5-triazine]. The three herbicides significantly increased the rate of apparent dominant lethals, but this reduction in egg hatch was probably due to physiologic toxicity to sperm. Atrazine significantly increased X-linked recessive lethals and X or Y loss after treatment by larval feeding. Injection of simazine elevated X-linked lethals, whereas treatment by larval feeding did not. None of these herbicides significantly increased partial loss of the Y chromosome nor sex chromosome nondisjunction. Much larger experiments are needed to determine with confidence the mutagenic potential of these herbicides.

Animals↗

Simazine toxicosis in sheep.

A case of simazine toxicosis in sheep was investigated. Affected animals exhibited generalized muscle tremors which progressed to mild tetany followed by collapse of the hind legs. Other signs included a short prancing gait with head tucked in a similar manner to that of a show pony. Death occurred within 2 to 3 d of the appearance of clinical signs. Mild to acute myocardial degeneration was evident; the livers had mild to acute hepatic fatty change. The levels of simazine found in livers varied from less than 0.2 mg/kg to almost 2 mg/kg in the worst affected animals.

Animals↗

[Immunochromatographic analysis of 2,4-dichlorophenoxyacetic acid and simazine using monoclonal antibodies labelled with colloidal gold].

A method of the competitive immunochromatographic assay of the pesticides 2,4-D (2,4-dichlorophenoxyacetic acid) and simazine (2-chloro-4,6-bis(N-ethylamino)-1,2,5-triazine) in aqueous samples was developed. Monoclonal antibodies to these pesticides labeled with colloidal gold were used to visualize the results. The sensitivity of the 2,4-D and simazine assay is 12 ng/ml, and the time of analysis is 3-7 min. The method does not differ in sensitivity from the competitive EIA using conjugates of monoclonal antibodies to the pesticides with horseradish peroxidase; however, the time of the EIA is 1.5 h. The immunochromatographic method of the pesticide detection is available and simple and may be recommended for the development of assays of any other low-molecular compounds. The English version of the paper: Russian Journal of Bioorganic Chemistry, 2004, vol. 30, no. 2; see also http://www.maik.ru.

2,4-Dichlorophenoxyacetic Acid↗

[Immunomorphological analysis of prolonged intoxication by low doses of herbicide simazine].

Dynamic investigation of several immunologic data and complex morphologic study of the thymus of rats fed for a long time (6 months) by very low doses of herbicide simazine have been carried out. Chronic simazine treatment resulted in the development of the secondary immunodeficient state with the damage of T lymphocytes. The morphologic signs of this process were the disarray in thymus structure (dystrophic changes and intercellular contact break of nurse cells, sclerosis of microvessel walls and stromal elements), severe decrease of the T lymphocyte number in peripheral blood, inhibition of phagocytosis reaction of neutrophils.

Animals↗

[The immunomorphological characteristics of a focal staphylococcal infection against a background of long-term exposure to low doses of simazine].

State of immunologic and nonspecific resistance of the organism, ultra- and histostructure of the thymus, histopathology of the wall of experimental staph abscess reproduced in animals given low doses of the herbicide simazine for a long time have been studied. It is established that simazine induced the immunodeficiency state underlain by pathologic changes in the thymus. Against this background experimental abscesses developed more rapidly, alterative and exudative processes in their wall proceeding more intensively and proliferative ones--attenuating. This provides prolongation of the abscesses healing phase for an indefinite time and chronization of the process.

Abscess↗