Rhizobium album sp. nov., isolated from a propanil-contaminated soil.

A novel Gram-stain negative, facultatively anaerobic, non-spore-forming, motile and rod-shaped bacterium (NS-104T) was isolated from a propanil-contaminated soil in Nanjing, China. Growth occurred at pH 5.0-9.0 (optimum 6.0), 16-37 °C (optimum 30 °C) and in the presence of 0-2.0% (w/v) NaCl (optimum, without NaCl). Strain NS-104T showed high 16S rRNA gene sequence identity to Rhizobium azooxidifex DSM 100211T (96.7%). The phylogenetic analysis of the 16S rRNA gene as well as the housekeeping genes recA, atpD and glnA demonstrated that strain NS-104T belongs to the genus Rhizobium. Strain NS-104T did not form nodules on six different legumes, and the nodD, nodC and nifH genes were neither amplified by PCR nor found in the draft genome of strain NS-104T. The sole respiratory quinone was ubiquinone Q-10. The polar lipid profile included the major amounts phosphatidylmonomethylethanolamine, phosphatidylglycerol and moderate amounts of phosphatidylethanolamine, phosphatidylcholine, diphosphatidylglycerol and unidentified aminolipids. The major cellular fatty acids were C18:1ω7c (39.6%), C19:0 cyclo ω8c (29.8%) and C16:0 (11.5%). The G + C content of strain NS-104T was 61.9 mol%. Strain NS-104T therefore represents a new species, for which the name Rhizobium album sp. nov. is proposed, with the type strain NS-104T (= KCTC 62327T = CCTCC AB 2017250T).

The fate of the herbicide propanil in plants of the littoral zone of the Three Gorges Reservoir (TGR), China.

The anti-seasonal hydrology with 30m water fluctuations in the Three Gorges Reservoir (TGR) of China attracts growing environmental and ecological concerns. We investigated the biotransformation of the herbicide propanil in plants dominating in the littoral zone of the TGR by applying the 14C-ring-labeled herbicide into non-aseptic hydroponic plant systems (Cynodon dactylon, Nelumbo nucifera and Bidens pilosa), aseptic plants (Lemna minor and Lemna gibba) and cell suspension cultures (C. dactylon and L. minor). (1) Propanil absorbed in plants of the hydroponic systems was (12.46±1.63)% of applied radioactivity (AR) (C. dactylon), (52.36±6.38)% (N. nucifera) and (76.55±6.07)% (B. pilosa), respectively. The 14C-residues in the plant extractable fractions and the corresponding media were confirmed by radio-Thin Layer Chromatography (TLC), radio-High Performance Liquid Chromatography (HPLC) and Gas Chromatography-Electron Ionization Mass Spectrometry (GC-EIMS) as propanil, 3,4-dichloroaniline (DCA) and N-(3,4-dichlorophenyl)-ß-d-glucopyranosylamine (Glu-DCA). (2) About 8% of AR was taken up by both aseptic plants, from which 7.0% of AR was extracted and identified also as propanil, DCA and Glu-DCA. (3) Concerning cell suspension cultures, (39.22±9.39)% of AR was absorbed by C. dactylon after 72hr, whereas the accumulated 14C-propanil by L. minor cell suspension culture amounted to (65.04±1.72)% after 7days. The identified compounds in cell cultures are consistent with those in the tested plants. Most of the pesticide residues in the intact plants were un-extractable, which are recognized as the end of the detoxification process. We therefore consider these plants as suitable for the phytoremediation of the herbicide propanil in the TGR region.

Estimation and Validation of Propanil Residues in Rice and Soil Samples by Gas Liquid Chromatography with Electron Capture Detector.

The purpose of this analysis was to develop an efficient analysis for the estimation of residues of propanil in rice grain, husk, straw and soil samples. A liquid-liquid partitioning method was used for the extraction of propanil residues from the rice grains and its contents. For this, representative 10 g samples of blended rice grain, husk, straw and soil were soaked in acetone for 24 h, and the contents then partitioned two times into 100 and 50 mL dichloromethane and one time with 100 mL hexane. The combined organic layers were collected and were concentrated to 10 mL acetone using a rotary vacuum evaporator at 40°C. The extract was then subjected to cleanup by dispersive solid phase extraction. The final extract was injected onto a GLC column, where the propanil residues were determined by electron capture detector. The percentage recoveries were ranged from 84.9 % to 98.3 % when samples were spiked at the levels of 0.05, 0.25 and 0.50 mg/kg. The limits of quantification and detection were 0.05 and 0.017 mg/kg, respectively.

Dissipation of propanil and 3,4 dichloroaniline in three different rice management systems.

This study focused on the dissipation of propanil and 3,4 dichloroaniline (3,4 DCA) over time in the soil, field water, inlet water, and outlet water of paddy fields under three management systems: conventional water seeding (CON), conventional water seeding with supplied liquid manure (LMA), and dry seeding (DRY). Propanil dissipation in water was also investigated under laboratory conditions. The field study was conducted from 2004 to 2006 at Vercelli, northern Italy. Propanil and 3,4 DCA showed rapid dissipation in water and soil environments both in the field and in the laboratory. Under controlled conditions, chemical hydrolysis was not detected for either compounds for up to 100 d at pHs of 5, 7, and 9. In the laboratory, the half-life of propanil in irrigation water was 1.1 d; its half-life in soil was routinely measured at <1.0 d (between 0.17 and 1.77 d). 3,4 DCA was found to persist much longer. Measured in all three study years at 50 d after treatment, its concentration ranged between 44 µg kg (CON) and 140 µg kg (DRY). Propanil and 3,4 DCA concentrations in paddy water were particularly high in samples collected at 4 d (2004) and 2 d (2005) after treatment. Maximum concentrations were 54.4 µg L (CON) for propanil (2005) and 113.7 µg L (LMA) for 3,4 DCA (2004). The concentrations of propanil and 3,4 DCA in inlet water were never above 1.1 and 0.3 µg L, respectively, whereas the highest concentration of each compound in outlet water was in samples collected first after treatment in 2005 and 2006. Both chemicals dissipated rapidly in all the soil-water environments but displayed no important differences among the three management systems. In conclusion, propanil and 3,4 DCA did not persist longer in paddy fields. A risk of water network contamination by these compounds may occur only early after herbicide spraying. A water-holding period after herbicide spraying may reduce this risk.

Propanil in a Manitoba soil: an interactive spreadsheet model based on conventional chemical kinetics.

An interactive spreadsheet model has been created for quantitative predictions of propanil sorption and reaction in a slurried Manitoba clay soil. Based on experimental values for the numbers of empty and filled sorption sites as reactants and products, the reaction mechanism has been described with conventional chemical kinetics. The on line HPLC µ extraction method revealed labile sorption, intraparticle diffusion, and a chemical reaction. Laidler's integral rate law for second order kinetics describes the labile sorption. Desorption, intraparticle diffusion, and the chemical reaction are all described by first order kinetics. The time dependent effects of initial concentration and amount of slurried soil can be predicted for sorption, intraparticle diffusion, and the amount of reaction product. Suggested applications include storm runoff and inputs for fate and transport hydrology models.

Pollution levels of thiobencarb, propanil, and pretilachlor in rice fields of the muda irrigation scheme, Kedah, Malaysia.

The purpose of this study was to investigate the potential risk of pretilachlor, thiobencarb, and propanil pollutants in the water system of the rice fields of the Muda area. The study included two areas that used different irrigation systems namely non-recycled (N-RCL) and recycled (RCL) water. Regular water sampling was carried out at the drainage canals during the weeding period from September to October 2006 in the main season of 2006/2007 and April-May 2007 in off season of 2007. The herbicides were extracted by the solid-phase extraction method and identified using a GC-ECD. Results showed that the procedure for identification of the three herbicides was acceptable based on the recovery test values, which ranged from 84.1% to 96.9%. A wide distribution pattern where more than 79% of the water samples contained the herbicide pollutants was observed at both the areas where N-RCL and RCL water was supplied for the two seasons. During September to October 2006, high weedicide residue concentration was observed at the N-RCL area and it ranged from 0.05 to 1.00 µg/L for pretilachlor and propanil and 10-25 µg/L for thiobencarb. In the case of the area with RCL water, the weedicide residue ranged from 1 to 5 µg/L for pretilachlor and propanil and 10-25 µg/L for thiobencarb. The highest residue level reached was 25-50, 50-100, and 100-200 µg/L for pretilachlor, propanil, and thiobencarb, respectively. During April to May 2007, high residue concentration frequently occurred at the area supplied with N-RCL irrigation water and it ranged from 0.05 to 1.00, 10 to 25, and 25 to 50 µg/L for pretilachlor, propanil, and thiobencarb, respectively. The highest residue level reached was 25-50 µg/L for pretilachlor and 100-200 µg/L for propanil and thiobencarb. There was an accelerated increase in the concentration of the herbicide residues, with the maximum levels reached at the early period of weedicide application, followed by a sharp decrease after the rice fields were completely covered with the rice crop. During the main season of 2006/2007, the concentration of propanil residue gradually rose, although that of the other herbicides declined.

Subcellular localization of the amide class herbicide 3,4-dichloropropionanilide (DCPA) in T cells and hepatocytes.

3,4-Dichloropropionanilide (DCPA), or propanil, a post-emergent herbicide used on rice and wheat crops in the United States, is immunotoxic in vivo and in vitro. Although it has been documented that DCPA exerts differential effects on specific immune cell types and is toxic to the liver, the way in which DCPA modulates intracellular functions leading to these effects is less understood. In this study, Jurkat T cells and hepatocytes from C57Bl/6 mice were exposed to 100 microM DCPA for 1.5 h. Following incubation, subcellular fractions of each cell type were isolated. DCPA, when present, was removed from each cell fraction by liquid-liquid extraction. The extraction product was then analyzed for the presence of DCPA using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The cellular uptake of DCPA was monitored by detection of the molecular ion and product ion of DCPA. The analyses demonstrate that DCPA, a lipophilic compound, localizes primarily in the cytosol of T cells and hepatocytes. These results indicate that DCPA is able to cross the plasma membrane and is accessible to intracellular immunomodulatory effectors.

Identifying major pesticides affecting bivalve species exposed to agricultural pollution using multi-biomarker and multivariate methods.

The aim of this investigation was to identify major pesticides that may cause detrimental effects in bivalve species affected by agricultural pollution. Investigations were carried out using freshwater clams (Corbicula fluminea) transplanted in the main drainage channels that collect the effluents coming from agriculture fields in the Ebro Delta (NE Spain) during the main growing season of rice (from May to August). Environmental hazards were assessed by measuring simultaneous up 46 contaminant levels and 9 biomarker responses. Measured biological responses showed marked differences across sites and months. Antioxidant and esterase enzyme responses were in most cases inhibited. Lipid peroxidation levels increased steadily from May in upstream stations to August in drainage channels. Principal Component (PCA) and Partial Least Squares to Latent Structure regression (PLS) analyses allowed the identification of endosulfan, propanil, and phenylureas as being the chemical contaminants causing the most adverse effects in the studied species.

Development and application of fluorescence sensor and test strip based on molecularly imprinted quantum dots for the selective and sensitive detection of propanil in fish and seawater samples.

Molecularly imprinted quantum dots (MIP-QDs) were successfully synthesized via reversed-phase microemulsion and used as the specific recognition element and signal probe of a fluorescence sensor or test strip to achieve the highly sensitive detection of propanil. The physical-chemical characteristics and excellent selectivity of MIP-QDs were elucidated. Under optimized parameters, the MIP-QDs had good linearity at the propanil concentration range of 1.0 µg/L to 20.0 × 103 µg/L by fluorescence quenching. The developed MIP-QD-based fluorescence sensor showed good recoveries ranging from 87.2 % to 112.2 %, and the relative standard deviation was below 6.0 % for the fish and seawater samples. In addition, the limits of detection (LODs) for fish and seawater were 0.42 µg/kg and 0.38 µg/L, respectively. The fluorescence test strip developed on the basis of the MIP-QDs also displayed satisfactory recoveries of 90.1 %-111.1 %, and the LOD for propanil in the seawater sample was 0.6 µg/L. The proposed fluorescence sensor and test strip were successfully used in propanil determination in environment and aquatic products.

Determination of antagonism between cyhalofop-butyl and other rice (Oryza sativa) herbicides in barnyardgrass (Echinochloa crus-galli).

Herbicide antagonism is defined as the reduction of control of certain weeds as the result of applying mixtures of two or more herbicides. Cyhalofop-butyl, a graminicide used for postemergence grass weed control in rice, is antagonized by some rice herbicides when applied simultaneously. The result of this type of antagonism usually results in decreased control of grass weeds. Research has shown that herbicide antagonism between graminicides and other herbicides may be caused by different mechanisms as the result of activity of the tank-mix partner. Using HPLC, the objective of this experiment was to analyze the fate of cyhalofop-butyl in barnyardgrass tissue when applied alone and in combination with halosulfuron, propanil, or triclopyr. Results indicated that absorption of cyhalofop-butyl and hydrolysis to its phytotoxic metabolite, cyhalofop-acid, was rapid and that halosulfuron and triclopyr had no effect. Because of a likely interaction of propanil with an apoplastic esterase enzyme, increased levels of cyhalofop-butyl and cyhalofop-acid were detected in barnyardgrass tissue, indicating that cyhalofop-butyl metabolism was hindered by propanil.

A new direct laser photo-induced fluorescence method coupled on-line with liquid chromatographic separation for the simultaneous determination of anilides pesticides.

A new direct laser photo-induced fluorescence high performance liquid chromatography (DL-PIF-HPLC) method is developed for the simultaneous determination of three anilide pesticides, namely carboxin, monalide and propanil. DL-PIF-HPLC uses a tunable Nd:YAG-OPO laser to obtain fluorescent photoproduct(s) and to simultaneously analyze their fluorescence in a short acquisition time with an intensified CCD camera, which improves the selectivity (by choosing the suitable excitation wavelength), increases the sensitivity (due to the high energy of the laser beam) and reduces the time of analysis, relative to the classical PIF methods. However, one of the main drawbacks of PIF methods is the presence of interferences with other compounds, such as other pesticides from the same group yielding similar fluorescent photoproducts, which reduces their selectivity. The analytical interest of DL-PIF-HPLC to avoid these interferences is demonstrated. The DL-PIF spectra, chromatographic conditions and analytical performances of DL-PIF-HPLC are presented for the simultaneous determination of three anilide pesticides. The calibration curves are linear over one order of magnitude and the limits of detection are in the ng mL(-1) range. The new DL-PIF-HPLC system has the advantage to combine the performances of both techniques, DL-PIF and liquid chromatography, and to improve the analysis selectivity.

Analysis of some pesticides in water samples using solid-phase microextraction-gas chromatography with different mass spectrometric techniques.

A solid-phase microextraction (SPME)-GC procedure has been developed for the analysis of four selected pesticides (propanil, acetochlor, myclobutanil and fenoxycarb) in water samples. Mass spectrometry (MS) was used and two different instruments, a quadrupole MS system and an ion trap operating in the MS-MS mode, were compared. A Carbowax-divinylbenzene SPME fiber was used. The performances of the two GC-MS instruments were comparable in terms of linearity (in the range of 0.1-10 microg/l in water samples) and sensitivity (limits of detection were in the low ng/l range); the quadrupole MS instrument gave better precision than the ion trap MS-MS system, but generally the relative standard deviations for replicates were acceptable for both instruments (<15%). Specificity with these two instruments was comparable in the analysis of ground water samples. Recovery tests were made to assess the applicability of the SPME procedure in the quantitative analysis of contaminated groundwaters.

Pesticide poisoning initially suspected as a natural death.

A pesticide poisoning victim suspected initially as having died a natural death was autopsied. The victim was a 47-year-old male. Macroscopically, signs of acute death and, in particular, general erosion in the mucosa of the airways and esophagus were observed. In the gastric contents, which had a pungent smell and a greenish-brown color, 5.00 g/L of propanil, 1.27 g/L of carbaryl, 0.38 g/L of ethylbenzene, and 0.32 g/L of xylene were detected. In the blood (serum), 21.6 mg/L of propanil, 8.1 mg/L of carbaryl, 1.7 mg/L of ethylbenzene, and 4.0 mg/L of xylene were identified. Postmortem methemoglobinemia (45%) was recognized. The cause of death was considered to have been pesticide poisoning; propanil was probably most responsible for his death. The police considered the case to be "death with illness as the suspected cause." By performing an autopsy, however, we were able to clarify that the cause of death was pesticide poisoning.

A comparison of electron-capture GLC, electrolytic-conductivity GLC and UV-absorption HPLC for the analysis of some herbicides in foods.

A comparison of gas chromatography with electron-capture or electrolytic-conductivity (nitrogen mode) detection, and high-pressure liquid chromatography (HPLC) with UV-absorption detection (254 nm) was carried out for the analysis of several herbicides in foods. Linuron, propanil, terbacil, benzoylprop-ethyl, and the fungicide DCNA in samples of cabbage, corn, potato, and wheat spiked at 2 and 0.2 ppm were examined. The pesticides were extracted with acetone, partitioned into petroleum ether-methylene chloride, and cleaned up on a 2% deactivated Florisil column before direct chromatographic analysis. Electron-capture gas-liquid chromatography (GLC) was most suitable for DCNA and benzoylprop-ethyl while UV-absorption HPLC was best for terbacil analysis. Linuron and propanil gave similar results for both electron-capture GLC and HPLC. Electrolytic-conductivity GLC could detect all pesticides at the 0.2 ppm level and exhibited the least number of extraneous peaks in the chromatograms.

Tetrachloroazobenzene in 3,4-dichloroaniline and its herbicidal derivatives: propanil, diuron, linuron, and neburon.

The presence of 3,3', 4,4'-tetrachloroazobenzene (TCAB) was determined by high performance liquid chromatography in 3, 4-dichloroaniline and herbicides made therefrom. The concentrations of TCAB in 3, 4-dichloroanilines and in different herbicides from a variety of manufacturers ranged from 9 to 1400 micrograms/g (ppm). The chloracnegenic potential of these products, as determined by rabbit ear test, suggests that it is in the same range of 2, 3, 7, 8-tetrachlorodibenzodioxin, a known potent chloracnegenic agent.

Reduced adsorption of propanil to black carbon: effect of dissolved organic matter loading mode and molecule size.

In the present study, the reduced adsorption of propanil on black carbon (BC) influenced by dissolved organic matter (DOM) was verified to be closely related to DOM molecule size and loading mode. Two congenetic carbons, a rice-residue-derived BC and the reduced product (RC), were characterized by similar specific surface area and different surface properties. Reduced product exhibits higher adsorption of propanil and DOM than BC. A series of model DOMs, including tannic acid (TA), pentagalloylglucose (PA), 3-O-galloylmucic acid (OA), and gallic acid (GA), characterized by different molecule sizes and molecular weights, were used to evaluate the different inhibitory effects. The DOM adsorption (mmol/g) on BC and RC follows the order of GA > PA > OA > TA, whereas the reduction of propanil adsorption influenced by the model DOM follows the order of PA ≈ TA > OA ≈ GA. The suppressive degree is connected to their molecule sizes rather than to molecular weights. Tannic acid and PA weakened propanil adsorption more effectively than OA and GA because the large DOM molecules may hinder propanil molecules into the micropore regions. Because of the similar molecule size, TA and PA present a similar suppressive effect on propanil adsorption. The influence of the DOMs was greater when preloaded than when in competition with propanil. The preloading of macromolecules (TA and PA) and OA on the carbons may lead to secondary and primary micropore blocks, respectively. The preloading of GA may cause partial GA molecule sequestration in the primary micropore, thus leading to strong attenuation of propanil adsorption on the carbons.

Integration of biological monitoring, environmental monitoring and computational modelling into the interpretation of pesticide exposure data: introduction to a proposed approach.

Open field, variability of climatic and working conditions, and the use of complex mixtures of pesticides makes biological and environmental monitoring in agriculture, and therefore risk assessment and management, very complicated. A need of pointing out alternative risk assessment approaches, not necessarily based on measures, but simple, user-friendly and reliable, feasible also in the less advanced situations and in particular in small size enterprises, arises. This aim can be reached through a combination of environmental monitoring, biological monitoring and computational modelling. We have used this combination of methods for the creation of "exposure and risk profiles" to be applied in specific exposure scenarios, and we have tested this approach on a sample of Italian rice and maize herbicide applicators. We have given specific "toxicity scores" to the different products used and we have identified, for each of the major working phases, that is mixing and loading, spraying, maintenance and cleaning of equipment, the main variables affecting exposure and inserted them into a simple algorithm, able to produce "exposure indices". Based on the combination of toxicity indices and exposure indices it is possible to obtain semiquantitative estimates of the risk levels experienced by the workers in the exposure scenarios considered. Results of operator exposure data collected under real-life conditions can be used to validate and refine the algorithms; moreover, the AOEL derived from pre-marketing studies can be combined to estimate tentative biological exposure limits for pesticides, useful to perform individual risk assessment based on technical surveys and on simple biological monitoring. A proof of principle example of this approach is the subject of this article.

High resolution mass spectrometric and high-field nuclear magnetic resonance spectroscopic studies of the herbicide propanil, its N-oxidative decomposition products and related compounds.

A number of compounds associated with dichloroaniline-based herbicides were examined by high resolution mass spectrometry and high-field nuclear magnetic resonance spectroscopy. These compounds included the herbicide propanil (N-propionyl-3,4-dichloroaniline) and the related compound N-acetyl-3,4-dichloroaniline. Several possible oxidative metabolic products, including N-hydroxy-3,4-dichloroaniline, nitroso-3,4-dichlorobenzene, N-hydroxy-N-propionyl-3,4-dichloroaniline and N-hydroxy-N-acetyl-3,4-dichloroaniline were also investigated. Mass spectral fragmentation schemes were proposed, based on exact mass measurements for fragment ions from these related compounds. The change in fragmentation behavior upon oxidation of the N-acyl compounds to N-hydroxy-N-acyl derivatives was found to be quite significant. The N-hydroxy-substituted compounds showed extensive fragmentation while the analogous non-hydroxylated compounds and nitroso-3,4-dichlorobenzene showed little fragmentation. Line broadening detected in several of the high-field nuclear magnetic resonance spectra was attributed to cis-trans isomerization. The highly toxic 3,3',4,4'-tetrachloroazobenzene and 3,3',4,4'-tetrachloroazoxybenzene were also examined by high resolution mass spectrometry.

Residual concentrations of propanil, TCAB, and other pesticides in rice-growing of soils in the United States, 1972.

Ninety-nine soil samples from the rice-growing states of Arkansas, California, Louisiana, Mississippi, and Texas were collected, primarily to monitor the herbicide propanil. No residual concentrations of propanil were detected in any of these samples, but TCAB, a propanil transformation product, was detected in six samples at concentrations ranging from 0.01 ppm to 0.05 ppm. Organochlorine and organphosphorus pesticide determinations were also performed. The compounds dieldrin, aldrin, and DDT and its metabolites were found more frequently; endrin and chlordane were found less frequently. The organophosphorus pesticides diazinon and parathion were detected occasionally.