Comparative hersistence of chlorpyrifos in a mineral soil after granular and drench applications

Abstract

Lorsban 15G (15% chlorpyrifos) at 1.6 and 2.2 g a.i./10 m row, and Lorsban 4E (40.7% chlorpyrifos) at 2.0 g a.i./10 m row were applied respectively to a silt loam soil as a band treatment at seeding and as a drench after seeding. The rate of disappearance of chlorpyrifos [Q,Q‐diethyl Q‐(3,5,6‐trichloro‐2‐pyridinyl) phosphorothioate] was relatively fast in the first 15 days but slowed down considerably thereafter regardless of the methods of application and application rates; and there was a statistically significant (p=0.05) linear relationship between the natural logarithm of chlopyrifos concentration and time. Based on the linear regression equations, the calculated pseudo‐first‐order rate constants were 0.041 day^‐1 and 0.044 day^‐1 respectively for the band treatments at 1.6 and 2.2 g a.i./10 m row; and 0.040 day^‐1 for the drench. The calculated half‐lives for all three treatments were similar and they ranged frcm 15.8 days to 17.3 days. The degradation product 3,5,6‐trichloro‐2‐pyridinol (TP) was detected in soil but not 3,5_/6‐trichloro‐2‐methoxypyridine (TMP). The concentration of TP increased steadily to a peak and declined thereafter. The highest mean concentration of TP was 2.21 ppm (dry wt) detected 29 days after band treatment at the high rate. After 90 days the concentration of TP decreased to 0.43 ppm (dry wt).     

Cometabolic degradation of acifluorfen by a mixed microbial culture

Abstract

Laboratory experiments were conducted to study the degradation of acifluorfen 5‐[2‐chloro‐4‐ (trifluoromethyl)‐phenoxy]‐2‐nitrobenzoic acid by a mixed microbial population.

Concentrations of acifluorfen up to 100 mg/1 had no inhibitory effect on the growth of microbial culture.

The microorganisms degraded acifluorfen through a cometabolic process in presence of 2‐nitrobenzoate.

The degradation rate of acifluorfen, determined by liquid chromatography analysis in batch cultures incubated under oxygen and oxygen‐limited conditions were compared. The degradation was slower under oxygen than oxygen‐limited conditions. Aminoacifluorfen was produced in both conditions.     

A rapid,colorimetric, procedure for determination of fenitrothion

Abstract

Fenitrothion in formulations and on grains is determined colorimetrically as 4‐nitro‐3‐methylphenoxide, after hydrolysis at room temperature catalysed by alkaline peroxide. Interferences in determination of residue levels are removed by filtration of commodity extract through basic alumina or by barium chloride plus excess oxidant.     

Potential of 2, 4‐dichlorophenoxyacetic acid conjugates as promutagens in the salmonella/microsome mutagenicity test

Abstract

Hepatic S9 preparations from Aroclor 1254 induced rats and 3‐methylcholanthrene induced woodchucks were used to investigate, in vitro, the mutagenic potential of five amino acid conjugates of 2, 4‐Dichlorophenoxyacetic acid (alanine, aspartic acid, leucine, methionine and tryptophan). Five strains of Salmonella typhimurium (TA97, TA98, TA100, TA1535, TA1538) were utilized for this purpose. Dose‐response effects producing a two‐fold increase of revertants over spontaneous levels were not observed with either S9 preparation indicating that the amino acid conjugates are not promutagens in these assays.     

Microbial degradation op tripluralin by aspergillus carneus,fusarium oxysporum and trichoderma viride ∗

Abstract

³H‐Trifluralin was synthesized by condensation of ³H‐4‐chloro‐3,5‐dinitro‐α, α, α‐trifluorotoluene with di‐n‐propylamine.

After incubation of trifluralin with Aspergillus carneus, Fusarium oxysporum and Trichoderma viride for 10 days, a small percentage (less than 10%) of unchanged herbicide was recovered in the extractable fraction. This indicates a fairly rapid degradation of the herbicide by the fungal species. Other than trifluralin, the culture medium contained at least five labelled products: 2, 6‐dinitro‐N‐n‐propyl‐α, α, α‐tri‐fluoro‐p‐toluidine; 2, 6‐dinitro‐α, α, α‐trifluoro‐p‐toluidine; 2‐amino‐6‐nitro‐α, α,‐trifluoro‐p‐toluidine, 2, 6‐dinitro‐4‐trifluoromethyl phenol and a major polar product which constituted more than 50% of the total extractable transformation products. A pathway, which similates that of aerobic degradation of the herbicide in soil, is suggested for the microbiological degradation of trifluralin.     

Evaluation of Beta‐naphthoxyacetic Acid for Mutagenic Activity in the Salmonella/mammalian Microsome Assay

1,3‐β‐d‐Glucan derived from baker's yeast was chemically modified in two steps yielding crosslinked carboxymethyl glucan as the sodium salt (2). After cation exchange with hexadecyltrimethylammonium chloride, a hydrophobic adsorbent (3) was obtained which showed an excellent binding of the estrogenic mycotoxin zearalenone with a maximum adsorption of up to 183 mg/g. Compound 3 additionally showed a relatively high adsorption capacity for the trichothecene T‐2 toxin of at least 10 mg/g. Starting from 2, various derivatives were prepared by cation exchange using quaternary ammonium salts bearing substituents besides methyl from four to 18 carbon atoms. The adsorption of T‐2 toxin on these derivatives were compared with compound 3 leading to the conclusion that 3 is the best adsorbent of all investigated tetraalkylammonium‐modified derivatives of 2.     

Determination of T‐2 toxin in grain and grain products by HPLC and TLC

Abstract

The purpose of this study was to investigate the T‐2 toxin contaminated grain and grain products consumed especially by Turkish population. The T‐2 toxin was detected using the high performance liquid chromatography (HPLC) with UV detector at 208 nm and the identify of T‐2 was further confirmed by thin layer chromatography (TLC). The recovery was 91 ±4.24% for corn flour fortified with the known amount of T‐2 toxin (1 ppm). The detection limits of T‐2 toxin for the HPLC and the TLC were 25 ng and 50 ng, respectively. A total of 30 commercially available grain and grain product samples were analyzed. Two corn flour samples were found to contain detectable levels of T‐2 toxin at a level of 1.60 ppm and 4.08 ppm.     

Subacute effects of a phosphorothionate pesticide on mixed function oxidases of wistar rats

Abstract

Subacute oral toxicity of a newly developed phosphorothionate insecticide (2‐butenoic acid‐3‐(diethoxy‐phosphinothioyl) methyl ester), coded as RPR‐2, was studied in male rats by oral (multiple) intubation of low (0.014 mg kg^‐1 day^‐1), medium (0.028 mg kg^‐1 day^‐1), and high (0.042 mg kg^‐1 day^‐1) dose for 90 days. The medium and high dose produced toxic symptoms along‐with some mortality (20%) occurred in the high dose treated rats. The medium and high doses caused significant inhibition in cytochrome P‐450 activity in liver, lung, kidney and brain tissues at 45 and 90 days. The high dose caused significant decrease in cyt.b₅ activity of all the four tissues at 45 and 90 days. Whereas, medium dose brought such effect in liver and lung at 45 and 90 days. Kidney and brain cyt.b₅ activity decreased significantly at 90^th day due to medium dose. Low dose also caused inhibition in cyt.b₅ activity in brain at 90^th day. Cytochrome P‐450 reductase activity was decreased significantly in liver, lung, kidney and brain at 45 and 90^th by the medium and high dose. The results indicated that RPR‐2 had potential to modulate hepatic and extra‐hepatic cyt.P‐450 dependent monooxygenase system of rat due to subacute exposure. These metabolic alterations were quite reversible after 28 days withdrawal of treatment.     

Short‐chain fatty acids affect cell‐association and invasion of HEp‐2 cells by Salmonella typhimurium

Abstract

This study demonstrates that the growth of S. typhimurium in Luria Bertani broth supplemented with acetate, propionate, butyrate, or a mixture of the three SCFA, affected cell‐association and the ability to invade cultured HEp‐2 cells. Cell‐association and invasion was determined after growth for 4 h of growth in the presence of the SCFA at pH 6 and 7. The results suggest that the growth rate of the culture may have affected cell‐association and invasion since accompanying the significant decrease in growth rate in the presence of SCFA at pH 6 was a decrease in cell‐association and invasion. However, the results also suggest that the individual SCFA may play a role in modulating cell‐association and the invasion phenotype and the regulation of cell‐association and invasion by the SCFA was dependent on the concentration and the pH of the medium. Although the growth rates were similar for S. typhimurium in the SCFA mixture, butyrate (100 mM) and propionate (50 mM) at pH 6, differences in cell‐association and invasion were observed among these cultures. Also, at pH 7, differences were observed among the SCFA treatments even though the growth rates were similar.     

Sorption of imidacloprid and its metabolites on tropical soils

Abstract

The sorption of imidacloprid (l‐[(6‐chloro‐3‐pyridinyl)‐methyl]‐N‐nitro‐2‐imidazolid‐inimine) (IMI) and its metabolites imidacloprid‐urea (l‐[(6‐chloro‐3‐pyridinyl)‐methyl]‐2‐imidazol‐idinone) (IU), imidacloprid‐guanidine (l‐[(6‐chloro‐3‐pyridinyl)‐methyl]‐4,5‐dihydro‐lH‐imidazol‐2‐amine) (IG), and imida‐cloprid‐guanidine‐olefin ( 1 ‐[(6‐chloro‐3‐pyridinyl)methyl]‐lH‐imidazol‐2‐amine) (IGO) was determined on six typical Brazilian soils. Sorption of the chemicals on the soil was characterized using the batch equilibration method. The range and order of sorption (Kd) on the six soils was IG (4.75–134) > IGO (2.87–72.3) > IMI (0.55 ‐16.9) > IU (0.31–9.50). For IMI and IU, Kd was correlated with soil organic carbon (OC) content and CEC, the latter due to the high correlation between OC and cation exchange capacity (CEC) (R²=0.98). For IG and IGO, there was no correlation of sorption to clay, pH, OC or CEC due to the high sorption on all soils. Average Koc values were IU = 170, IMI = 362, IGO = 2433, and IG = 3500. Although Kd and Koc values found were consistently lower than those found in soils developed in non‐tropical climates, imidacloprid and its metabolites were still considered to be slightly mobile to immobile in Brazilian soils.     

Differential enhanced degradation of cis‐ and trans‐1,3‐D in soil with a history of repeated field applications of 1,3‐D

Abstract

The fumigant 1,3‐dichloropropene (1,3‐D) is considered to be a potential alternative to methyl bromide. The degradation rates of cis‐ and trans‐l,3‐D in soil from a treated site during three successive annual applications of 1,3‐D progressively increased with an increase in the number of annual applications. The enhancement was greater for trans‐l,3‐D degradation than cis‐l,3‐D. In untreated soil, the degradation rates of the two isomers were similar. The enhancement lasted slightly longer than 2 years after annual field application of 1,3‐D had ceased. A single field reapplication of 1,3‐D to the treated site that had not been treated for 2 years resulted in resumed differential enhanced degradation of cis‐ and trans‐l,3‐D. Microorganisms were responsible for the enhanced degradation.     

N1‐aryl‐N2‐dichloroacetyl glycine and alanineamides as selective safeners for corn against chloroacetanilide herbicides

Abstract

Structurally new N¹aryl‐N²‐dichloroacetyl glycine and alaninamides were prepared. Greenhouse experiments were conducted to determine the effectiveness of the new compounds in protecting corn seedlings from chloroacetanilide (acetochlor, alachlor, dimethachlor, metazachlor, metolachlor) injury using dichlormid and BASF‐145138 as standard safeners. High rates of chloroacetanilides caused significant injury to sensitive corn hybrids. The most acive derivatives reduced injury to corn from dimethachlor and metolachlor and lesser extent from acetochlor and metazachlor. The most effective derivatives of the new compounds displayed better safening activity than the standards. Some of the new compounds were found to be selective safeners when formulated as a tank mixture with metolachlor in a 1:33–100 safener‐to‐herbicide ratio showing the same or better activity than the standard used.

Nomenclature: BASF‐145138, 1‐dichloroacetyl‐hexahydro‐3,3,8α‐trimethyl‐pyrrolo‐[1,2‐α]—pyrimidin‐6‐(2H)‐one; EPTC, S‐ethyl‐N,N‐dipropylcarbamothioate; dichlormid, 2,2‐dichloro‐N,N‐di‐2‐propenyl acetamide; corn, Zea Mays L. ‘Pannonia SC’.     

Removal of 2, 4‐D from aqueous solution by the adsorbents from spent bleaching earth

Abstract

The removal of 2, 4‐D (2, 4‐ dichlorophenoxyacetic acid) from aqueous solutions by activated spent bleaching earths (SBE) was studied at 20 °C. Experiments were performed as a function of time, initial concentration, dose and particle size of the adsorbent. The Langmuir and Freundlich adsorption equations were fitted by the adsorption data obtained. The values of Langmuir and Freundlich constants were determined. The adsorption kinetic was found to follow Lagergren equation. Both the boundary layer and intraparticle diffusion played important roles in the adsorption rate of 2, 4‐D. As the size of the adsorbent increased, the time to reach equilibrium increased but adsorption capacity decreased.     

The metabolism of neonicotinoid insecticide thiamethoxam by soil enrichment cultures,and the bacterial diversity and plant growth‐promoting properties of the cultured isolates

A soil enrichment culture (SEC) rapidly degraded 96% of 200 mg L^?1 neonicotinoid insecticide thiamethoxam (TMX) in MSM broth within 30 d; therefore, its metabolic pathway of TMX, bacterial diversity and plant growth‐promoting rhizobacteria (PGPR) activities of the cultured isolates were studied. The SEC transformed TMX via the nitro reduction pathway to form nitrso, urea metabolites and via cleavage of the oxadiazine cycle to form a new metabolite, hydroxyl CLO‐tri. In addition, 16S rRNA gene‐denaturing gradient gel electrophoresis analysis revealed that uncultured rhizobacteria are predominant in the SEC broth and that 77.8% of the identified bacteria belonged to uncultured bacteria. A total of 31 cultured bacterial strains including six genera (Achromobacter, Agromyces, Ensifer, Mesorhizobium, Microbacterium and Pseudoxanthomonas) were isolated from the SEC broth. The 12 strains of Ensifer adhaerens have the ability to degrade TMX. All six selected bacteria showed PGPR activities. E. adhaerens TMX‐23 and Agromyces mediolanus TMX‐25 produced indole‐3‐acetic acid, whereas E. adhaerens TMX‐23 and Mesorhizobium alhagi TMX‐36 are N₂‐fixing bacteria. The six‐isolated microbes were tolerant to 200 mg L^?1 TMX, and the growth of E. adhaerens was significantly enhanced by TMX, whereas that of Achromobacter sp. TMX‐5 and Microbacterium sp.TMX‐6 were enhanced slightly. The present study will help to explain the fate of TMX in the environment and its microbial degradation mechanism, as well as to facilitate future investigations of the mechanism through which TMX enhances plant vigor.     

Degradation of telone II in contaminated and noncontaminated soils

Abstract

Degradation of the nematicide Telone II (cis‐ and trans‐1,3‐dichloropropene comprise the active ingredients) in soil was studied using ¹⁴C‐l,3‐dichloropropene (DCP) along with soil samples collected from a field test site near Quincy, Florida. A mixed bacterial culture isolated from the soil in the presence of a second carbon source, glucose or yeast extract, completely degraded ¹⁴C‐DCP to ¹⁴CO₂, water‐soluble products, and microbial mass. ¹⁴C‐DCP in soil was also degraded to ¹⁴CO₂. After 28 days of incubation, the labeled chemical was completely degraded to ¹⁴CO₂, water‐soluble metabolites, bound‐residues, and possibly some microbial mass. Little or no difference was observed in the degradation of ¹⁴C‐DCP in soil samples collected one week prior to field application of Telone II, or two weeks and two years after application.     

The effects of triclopyr on 2,4‐D mineralization in two soils

Abstract

The effects of the herbicide triclopyr (3,5,6‐trichloro‐2‐pyridinyloxyacetic acid) on the mineralization of 2,4‐D (2,4‐dichlorophenoyxacetic acid) in two soils which differed in their histories of prior exposure to the two herbicides were investigated. The relative effects of triclopyr on 2,4‐D mineralization and most probable numbers of 2,4‐D degraders were dependent upon the soil. Triclopyr was shown to increase 2,4‐D mineralization rates in a soil which had been exposed to both 2,4‐D and triclopyr, but decreased the mineralization rate of 2,4‐D and inhibited the increase of most probable numbers of 2,4‐D degraders in a soil that had not been directly exposed to either herbicide.     

Distribution and persistence of carbaryl in some terrestrial and aquatic components of a forest environment

Abstract

An oil‐based formulation of carbaryl (1‐naphthyl N‐methyl‐carbamate) (Sevin‐2‐Oil) was applied twice by a fixed‐wing aircraft at a dosage rate of 280 g of A.I./ha/application to a coniferous forest near Allardville, New Brunswick. The highest concentrations of the chemical in fir foliage, litter and forest soil 1 h after application were respectively 4.20, 1.21 and 0.59 ppm (fresh weight). The residues dissipated rapidly and the DT50 values obtained from the depletion curves were 2.3 d for foliage and 1.5 d for litter and soil samples. Very low levels (<0.1 ppm) of carbaryl persisted in foliage and litter beyond the 10 d sampling period. The maximum residue level found in stream water was 0.314 ppm and more than 50% of it had dissipated within 1 h. Low but detectable levels (0.001 ppm) of the chemical persisted in water until the end of the 10 d sampling period. Sediment samples contained a maximum level of 0.04 ppm, which dissipated below the detection limit within 5 h. Brook trout and slimy sculpins captured in the stream 1 d after the spray contained on average about 0.04 ppm of carbaryl and none of it was found in 3 d postspray samples.     

An alternative supercritical fluid extraction system for aqueous matrices and its application in pesticides residue analysis

Abstract

Supercritical fluid extraction (SFE) is a rapid and convenient method for the isolation of organic compounds from environmental samples. This paper describes a supercritical carbon dioxide (CO₂) extraction system that uses a newly designed extraction cell to recover organic compounds from an aqueous matrix. Analysis of the extracts by gas chromatography‐electron capture detector (GC‐ECD) indicated that the herbicide trifluralin (2,6‐dinitro‐N,N‐dipropyl‐4‐trifluoromethylaniline) could be quantitatively extracted by using the SFE system proposed with small amounts of sample. The percentage of recovery obtained with the SFE system described was twice as high as the result obtained using a conventional solid‐phase extraction technique. Extraction by SFE was completed in a short period of time using a simple and low‐cost home‐made system that did not require the use of organic solvents.     

Chloromuconolactone dehalogenase ClcF of actinobacteria

This work investigated the distribution of the clcF gene in actinobacteria isolated from different ecotopes. The gene encodes chloromuconolactone dehalogenase (CMLD) ClcF, the enzyme found to date in only one representative of Gram‐positive bacteria, Rhodococcus opacus 1CP, adapted to 2‐chlorophenol (2CP). Using primers specific to the clcF gene, from the DNA matrix of rhodococcal strains closely related to species Rhodococcus wratislaviensis (P1, P12, P13, P20, G10, KT112, KT723, BO1) we obtained PCR products whose nucleotide sequences were 100% identical to that of the clcF gene from strain R. opacus 1CP. CMLDs isolated from the biomass of strains Rhodococcus spp. G10 and P1 grown on 2CP did not differ by their subunit molecular mass deduced from the known amino acid sequence of the clcF gene from the ClcF of strain R. opacus 1CP. Matrix‐assisted laser dissociation/ionization time‐of‐flight mass spectrometry showed the presence of a peak with m/z 11,194–11,196 Da both in whole cells and in protein solutions with a ClcF activity. Thus, we have first time shown the distribution of ClcF among actinobacteria isolated from geographically distant habitats.     

The electron density distribution in pyridinium and bipyridylium compounds and its relevance to their adsorption by expanding lattice clays

Abstract

Charge distributions in 1, 1'‐ethylene‐2, 2'‐bipyridylium (diquat), 1,1'‐dimethyl‐4,4'‐bipyridylium (paraquat) and 1‐methylpyridinium organocations were calculated by a Complete Neglect of Differential Overlap semi‐empirical quantum mechanical procedure. The data show that the positive charges in the organocations are distributed around the molecules and are greatest in the positions ortho and para to the heterocyclic nitrogen atoms. Earlier interpretations of the mechanisms of adsorption of paraquat and diquat by soils and clays assumed that the charges were located in the heterocyclic nitrogen atoms. Here some consideration is given to the influence of the charge delocalizations on the processes of adsorption by montmorillonite and vermiculite clay preparations.