Mineralization of soil-aged isoproturon and isoproturon metabolites by Sphingomonas sp. Contribution of non-agricultural pesticides to pesticide load in surface water. Also, it is possible to deduce that electrophilic attacks on 4C would cause the elimination of the metoxi-1-metilurea moiety. Evaluating non-equilibrum herbicides transport in undisturbed grassed buffer strips soil columns. Biology Laboratory, A member of the class of phenylureas that is 1,1-dimethylurea substituted by a, InChI=1S/C12H18N2O/c1-9(2)10-5-7-11(8-6-10)13-12(15)14(3)4/h5-9H,1-4H3,(H,13,15), 1,1-dimethyl-3-[4-(propan-2-yl)phenyl]urea. Dihedral angle 2C-4C-10N-12C = 17.53, 10N-12C-13N-21O = 18.34. The purpose of the fee is to recover costs associated The optimized molecules in the gas phase were further reoptimized at the B3LYP/6-311++G(2d,2p) level employing the PCM solvation model [62, 63], with the dielectric constant 78.5 for water at 25C. Also, it is important to mention that because of their low volatility, slow biodegradation, and low sorption in soils, PHUs have been frequently detected in surface, ground, and even drinking water [5], by which they have the potential to impact ground water quality [6]. Optimized structure of isoproturon at the MP2/6-311++G(2d,2p) level of theory. We have calculated global and local DFT reactivity descriptors for isoproturon, diuron, linuron, and chlorotoluron herbicides at the MP2/6-311++G(2d,2p) level of theory. Second row atoms, Z=1118,, S. Miertus and J. Tomasi, Approximate evaluations of the electrostatic free energy and internal energy changes in solution processes,, S. Miert, E. Scrocco, and J. Tomasi, Electrostatic interaction of a solute with a continuum. Original file (SVG file, nominally 231 378 pixels, file size: 27 KB). Thus, nucleophilic and free radical attacks on diuron and linuron would cause a substitution of the hydrogen atom on 7C, while electrophilic attacks on diuron and chlorotoluron would cause the elimination of the dimethylurea fragment. Although, there are so far no reported incidences of human poisoning, based on effects seen in animals, acute exposure to PHUs would be expected to cause mild skin irritation and headaches, drowsiness, and lack of coordination [13]. The influence of lipophilicity and formulation on the distribution of pesticides in laboratory-scale sediment/water systems. A multi-residue method for characterization and determination of atmospheric pesticides measured at two French urban and rural sampling sites. CopyCopied, CSID:33695, http://www.chemspider.com/Chemical-Structure.33695.html (accessed 20:42, Jul 29, 2022) Pesticide degradation in a 'biobed' composting substrate. Source; quality score; and other information, Solubility - In water at 20 C (mg l), Solubility - In organic solvents at 20 C (mg l), Octanol-water partition coefficient at pH 7, 20 C, Henry's law constant at 25 C (Pa m mol), Maximum UV-vis absorption L mol cm, 207.8nm = 32512, 241.5nm = 1972, 295nm = 550, EU dossier lab studies DT range 7.2-18.2 days, DT = 23.8-111.1 days, field studies DT range 12-33 days, DT range 34-68 days, Dissipation rate RL on plant matrix, Dissipation rate RL on and in plant matrix, Published literature RL range 1.5-7.5 days, wheat, whole plant, n=2, Aqueous photolysis DT (days) at pH 7, Aqueous hydrolysis DT (days) at 20 C and pH 7, pH sensitive: DT 1210 days at pH 5, 540 days at pH 9, all at 25 C, SCI-GROW groundwater index (g l) for a 1 kg ha or 1 l ha application rate, Potential for particle bound transport index, Mammals - Acute oral LD (mg kg), Mammals - Chronic 21d NOAEL (mg kg bw d), Birds - Short term dietary (LC/LD), Birds - Chronic 21d NOEL (mg kg bw d), Earthworms - Acute 14 day LC (mg kg), Earthworms - Chronic NOEC, reproduction (mg kg), Nitrogen mineralisation: No significant adverse effect, Contact acute LD (worst case from 24, 48 and 72 hour values - g bee), Oral acute LD (worst case from 24, 48 and 72 hour values - g bee), Unknown mode acute LD (worst case from 24, 48 and 72 hour values - g bee), Acute LD (worst case from 24, 48 and 72 hour values - g insect), Beneficial insects (Lacewings) as % Mortality at dose 1.5 kg ha, Beneficial insects (Parasitic wasps) as % Mortality at dose 25 kg ha, Beneficial insects (Predatory mites) as % Mortality at dose 25 kg ha, Fish - Acute 96 hour LC (mg l), Aquatic invertebrates - Acute 48 hour EC (mg l), Aquatic invertebrates - Chronic 21 day NOEC (mg l), Aquatic crustaceans - Acute 96 hour LC (mg l), Sediment dwelling organisms - Acute 96 hour LC (mg l), Sediment dwelling organisms - Chronic 28 day NOEC, static, water (mg l), Sediment dwelling organisms - Chronic 28 day NOEC, sediment (mg kg), Aquatic plants - Acute 7 day EC, biomass (mg l), Algae - Acute 72 hour EC, growth (mg l), Algae - Chronic 96 hour NOEC, growth (mg l), Threshold of Toxicological Concern (Cramer Class), Mammals - Dermal LD (mg kg body weight), Mammals - Inhalation LC (mg l), ADI - Acceptable Daily Intake (mg kg bw day), ARfD - Acute Reference Dose (mg kg bw day), AAOEL - Acute Acceptable Operator Exposure Level (mg kg bw day), AOEL - Acceptable Operator Exposure Level - Systemic (mg kg bw day), No unacceptable risks to bystanders identified, No unacceptable risks to operators or other workers identified, Mammalian dose elimination route and rate, Endocrine issues - Pregnane X cellular receptor activation. The Fukui function can be written as [56]where is the electronic density. On the other hand, the atom 7C is susceptible to either nucleophilic or free radical substitutions. Study of solubility of isoproturon by its complexation with beta-cyclodextrin. 1SD, UK +44 (0)1223 49 44 44, Copyright EMBL-EBI 2018 | EBI is an outstation of the European Molecular This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Specifically, the PUHs 3-(4-isopropylphenyl)-1,1-dimethyl urea (isoproturon), 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron), 3-(3,4-diclorofenil)-1-metoxi-1-metilurea (linuron), and 3-(3-chloro-p-tolyl)-1,1-dimethylurea (chlorotoluron) are slowly degraded in water and are quite persistent [8, 9], and it is increasingly common to find their parent compounds and metabolites in groundwater in concentrations exceeding the drinking water threshold limit of 0.1gL1 [10, 11]. Effect of different soil textures on leaching potential and degradation of pesticides in biobeds. The energy value of the vertical electronic affinity () can be calculated as , where and are the total ground-state energies in the neutral and singly charged configurations. Phenylurea herbicides (PUHs) are an important group of pesticides which have been broadly used in agriculture. Modeling of an annular photocatalytic reactor for water purification: oxidation of pesticides. Copyright for NIST Standard Reference Data is governed by EU Annex III PIC DGD) (, R = Peer reviewed scientific publications, L = Pesticide manuals and hard copy reference books / other sources, A = Chromosome aberration (EFSA database), E = Unspecified genotoxicity type (miscellaneous data source), (Also known as: IPU; ipuron; CGA 18731; AE F016410), A herbicide for use, typically, in cereals to control annual grasses and many broad-leaved weeds, Cereals including wheat, barley, rye; Rice-wheat cropping systems, EC Regulation 1107/2009 (repealing 91/414), Approved for use () under EC 1107/2009 in the following EU Member States, International Chemical Identifier key (InChIKey), International Chemical Identifier (InChI), InChI=1S/C12H18N2O/c1-9(2)10-5-7-11(8-6-10)13-12(15)14(3)4/h5-9H,1-4H3,(H,13,15), Cambridge Crystallographic Data Centre diagrams. Dihedral angle 12C-11C-6C-3C = 0.2, 2C-4C-20N-22C = 22.03. I. If the file has been modified from its original state, some details such as the timestamp may not fully reflect those of the original file. CopyCopied, Validated by Experts, Validated by Users, Non-Validated, Removed by Users, Predicted data is generated using the ACD/Labs Percepta Platform - PhysChem Module, Predicted data is generated using the US Environmental Protection Agencys EPISuite, Click to predict properties on the Chemicalize site, For medical information relating to Covid-19, please consult the, https://www.ebi.ac.uk/chebi/searchId.do?chebiId=CHEBI:6049, ACD/Labs Percepta Platform - PhysChem Module, US Environmental Protection Agencys EPISuite, Compounds with the same molecular formula, Search Google for structures with same skeleton. Evolution over time of the agricultural pollution of waters in an area of Salamanca and Zamora (Spain). All the calculations here reported were performed with the package Gaussian 09 [65] and visualized with GaussView V. 2.08 [66]. InChI=1S/C12H18N2O/c1-9(2)10-5-7-11(8-6-10)13-12(15)14(3)4/h5-9H,1-4H3,(H,13,15). on behalf of the United States of America. Using a linked soil model emulator and unsaturated zone leaching model to account for preferential flow when assessing the spatially distributed risk of pesticide leaching to groundwater in England and Wales. Therefore, Hirshfeld partitioning scheme was used to derive the atomic charges at the MP2/6-311++G(2d,2p) level. N,N-dimethyl-N'-(4-(1-methylethyl)phenyl)urea, WFD priority substance; Potential groundwater contaminant, Relevant Environmental Water Quality Standards, EU Directive 2008/105/EC EQS surface waters: annual average 0.3 g l; max measured 1.0 g l, Herbicide Resistance Classification (HRAC), Herbicide Resistance Classification (WSSA), Insecticide Resistance Classification (IRAC), Fungicide Resistance Classification (FRAC), Example manufacturers & suppliers of products using this active now or historically. Global reactivity descriptors for isoproturon, chlorotoluron, diuron, and linuron at the MP2/6-311++G(2d,2p) level of theory, in the aqueous phase. rupting properties. Effect of soil composition and dissolved organic matter on pesticide sorption. [40], respectively. Determination of solid-liquid partition coefficients (Kd) for the herbicides isoproturon and trifluralin in five UK agricultural soils. Modeling of single-step and multistep adsorption isotherms of organic pesticides on soil. Also, the structures optimized at the B3LYP/6-311++G(2d,2p) level were further reoptimized at the MP2/6-311++G(2d,2p) level in the aqueous phase; see Figures 1, 2, 3, and 4. A selective, systemic herbicide used to control annual grasses and broadleaf However, it is important to evaluate local reactivity descriptors as the condensed Fukui function to analyze the pinpoint distribution of the reactivity in the molecule in order to propose specific degradation mechanisms. docrine-disrupting properties. Evaluation and characterization of a commercial immunosorbent cartridge for the solid-phase extraction of phenylureas from aqueous matrices. Additional to the global reactivity parameters, it has been possible to define local reactivity parameters [52, 53], such as the Fukui Function () [54, 55]. A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects,, M. Head-Gordon, J. The vibrational frequencies were computed to make sure that the stationary points were minima in the potential energy surface. Optical whole-cell biosensor using Chlorella vulgaris designed for monitoring herbicides. These values compare favorably with those values reported in the literature for phenylurea compounds [67, 68]. In order to take into account the effect of solvation on the electronic properties of isoproturon, diuron, linuron, and chlorotoluron, the optimized structures in the gas phase were used as starting point to reoptimize them at the B3LYP/6-311++G(2d,2p) level without any symmetry constraints employing the PCM solvation model. Database and to verify that the data contained therein have In this sense a detailed knowledge of the reactivity exhibited by isoproturon, diuron, linuron, and chlorotoluron at the molecular level may become fundamental to recognize their degradation mechanism in aqueous conditions. Simultaneous multi-analyte determination of estrone, isoproturon and atrazine in natural waters by the RIver ANAlyser (RIANA), an optical immunosensor. The chemical potential can be related to the escaping tendency of an electron and is characteristic of the molecular electronegativity [48], while has been related to the polarizability of the molecular system [49, 50]. been selected on the basis of sound scientific judgment. It is important to mention that the values of the Fukui function are dependent on the scheme of charges used. A member of the class of phenylureas that is 1,1-dimethylurea substituted by a p-cumenyl group at position 3. A = EU regulatory and evaluation data as published by EC, EFSA (RAR, DAR & Conclusion dossiers), EMA (e.g. An absence of an alert does not imply the substance has no implications for human health, biodiversity or the environment but just that we do not have the data to form a judgement. The Fukui function values for chlorotoluron are reported in Figure 6; note that the distribution of the more reactive sites for this herbicide are located on 4C, 7C, and 7C atoms for electrophilic, nucleophilic, and free radical attacks, respectively. Solid-phase extraction and sample stacking-micellar electrokinetic capillary chromatography for the determination of multiresidues of herbicides and metabolites. Also, note that chlorotoluron exhibits the lower value of which indicates that it is better nucleophile in comparison to isoproturon, diuron, and linuron. In soils, it has been observed that these herbicides may be degraded through demethylation at the urea nitrogen by mean enzymatic and microbial activity [34]. U.S. Department of Health and Human Sevices. Note that , , and are global type response functions that characterize the molecule as a whole which allow us to characterize global reactivity trends [41]. Click on a date/time to view the file as it appeared at that time. In Table 1, the values of the electronic energies calculated for these herbicides with the charges +1, 0, and 1 are reported, which correspond to the cationic, neutral, and anionic species, respectively. Luis Humberto Mendoza-Huizar wishes to thank National Laboratory for the Characterization of Physicochemical Properties and Molecular Structure (LACAPFEM) for providing supercomputing time. Public Health Service. Real, Removal of phenylurea herbicides from waters by using chemical oxidation treatments,, M. Kaur, A. K. Malik, and B. Singh, Determination of phenylurea herbicides in tap water and soft drink samples by HPLC-UV and solid-phase extraction,, J. M. Sanchis-Mallols, S. Sagrado, M. J. Medina-Hernndez, R. M. Villanueva Camaas, and E. Bonet-Domingo, Determination of phenylurea herbicides in drinking waters by HPLC and solid phase extraction,, N. Badawi, S. Rnhede, S. Olsson et al., Metabolites of the phenylurea herbicides chlorotoluron, diuron, isoproturon and linuron produced by the soil fungus, M. Carrier, M. Besson, C. Guillard, and E. Gonze, Removal of herbicide diuron and thermal degradation products under Catalytic Wet Air Oxidation conditions,. Data Program, but require an annual fee to access. Data from NIST Standard Reference Database 69: The National Institute of Standards and Technology (NIST) weeds in cereals, its use within the EU has been banned after September 2017 on the grounds of potential groundwater contamination and risks to aquatic life; there have also been concerns about its en A comparative study,, F. L. Hirshfeld, Bonded-atom fragments for describing molecular charge densities,, J. Padmanabhan, R. Parthasarathi, U. Sarkar, V. Subramanian, and P. K. Chattaraj, Effect of solvation on the condensed Fukui function and the generalized philicity index,.