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.     

Accelerated degradation of carbofuran in standing water from carbofuran‐retreated Azolla plots

Abstract

Carbofuran (2, 3‐dihydro‐2, 2‐dimethyl‐7‐benzofuranyl N‐methylcarbamate) was mixed with standing water from six flooded Azolla (a fern harboring a nitrogen fixing alga, Anabaena azollae) plots that had been regularly treated with carbofuran before. The insecticide completely disappeared in 5 to 10 days when mixed with water from three of the six plots. The enrichment culture, prepared by further additions of carbofuran to the standing water from an Azolla plot, degraded bendiocarb (2, 2‐dimethyl‐l, 3‐benzidioxol‐4‐yl‐N‐methylcarbamate), carbofuran and carbosulfan [2,3‐dihydro‐2,2‐dimethyl‐7‐benzofuranyl (di‐n‐butyl‐aoinosulfenyl) methyl‐carbamate ] in that order. Enrichment culture, upon sterilization by autoclavlng, lost its ability to degrade carbofuran. Evidently, accelerated degradation of carbofuran in standing water from retreated Azolla plots was mediated by microorganisms.     

Contributions to ecological chemistry CXII balance of conversion of buturon‐14C in wheat under outdoor conditions 1

Abstract

The urea herbicide buturon (N‐[p‐chlorophenyl] ‐N’ ‐methyl‐N’ ‐isobutinyl‐urea), ¹⁴C‐labeled, was sprayed on winter wheat as an aqueous formulation (2.98 kg/ha) under outdoor conditions. Upon harvest (three months after application), a total of 49. 2% of the applied radiocarbon was recovered: 2.0% in the plants, 46.9% in the soil, and 0.3% in the leaching water (depth > 50 cm); less than 0.1% was in the grains (0.464 ppm). Only about half of the radioactivity present in plants could be recovered under mild extraction conditions; about half of this was unchanged buturon. In straw and husk extracts, the following metabolites were identified by gaschromatography/mass spectrometry: N‐(p‐chlorophenyl)‐N‐methyl‐O‐methyl‐carbamate (metabolite I), N‐phenyl‐N’ ‐formyl‐urea (metabolite II), two unstable metabolites giving (p‐chlorophenyl)‐isocyanate upon purification (metabolites III and IV), N‐(p‐chlorophenyl)‐N’ ‐methyl‐N’ ‐isobutenylol‐urea (metabolite V), p‐chloroformanilide (metabolite VI) and biologically bound p‐chloroaniline (metabolite VII). In the root and basal stem extract, the following metabolites were identified by gas chromatography/mass spectrometry: N‐(p‐chlorophenyl)‐O‐methyl‐carbamate (metabolite VIII) and N‐(p‐chlorophenyl)‐N’ ‐methyl‐urea (metabolite IX).     

Ochratoxin A and Penicillic acid interaction in mice

Abstract

Penicillic Acid (PA) and Ochratoxin A (OA) are toxic fungal metabolites that are synergistic in combination. This interaction was investigated using mice which were dosed orally as follows: control, none; solvent control, 0.2 ml bicarbonate buffer; PA, 40 mg/kg; OA, 10 mg/kg and combination, 40 mg/kg PA + 10 mg/kg OA. The only significant histopathologic change observed was an acute multifocal toxic tubular nephrosis which appeared most severe in the combination‐treated mice killed on day 10. While the combination group had a death rate of 20% (5/25), no deaths occurred in the other treatment groups. The increased death rate and the extensive nephrotoxic findings in the combination group indicate a toxic interaction between OA and PA at sub‐lethal dose levels and is consistent with a renal site of action.     

Monitoring of pesticide residues in a cotton crop soil

Abstract

This paper reports on the residues of methyl parathion (O,O‐dimethyl O‐4‐nitrophenyl phosphorothioate), trifluralin (α, α, α‐trifluoro‐2, 6‐dinitro‐N, N‐dipropyl‐p‐toluidine), endosulfan [(1, 4, 5, 6, 7, 7‐hexachloro‐8, 9, 10‐trinorborn‐5‐en‐2, 3‐ylenebismethylene) sulfite] and dimethoate (O, O‐dimethyl S‐methylcarbamoylmethyl phosphorodithioate) in a cotton crop soil. Soil samples (0–15 cm) were collected at different periods from the cotton crop farm and subjected to Soxhlet extraction. The extracted material was analysed after clean‐up by a HP5890 II gas Chromatograph equipped with a ⁶³Ni electron‐capture detector (ECD‐⁶³Ni) and fitted with a 25m x 0,2mm i.d. fused silica capillary column [Ultra‐2 (5% phenylmethyl polysiloxane)]. The recoveries of the pesticide residues from the spiked control soil were determined after Soxhlet extraction and C₁₈ cartridges clean‐up by using radiotracer techniques with the corresponding ¹⁴C‐pesticides. The results show that in the cotton crop soil the pesticide residues under study were present in the range of 0.1 to 0.4 mg ? kg^‐1. Endosulfan was found to be rapidly degraded in the soil and formed a sulfate metabolite.     

Excretion balance,metabolic fate and tissue residues following treatment of rats with amitraz and N‘‐ (2,4‐dimethylphenyl)‐N‐methylformamidine

Abstract

Amitraz and its metabolite N‘‐ (2,4‐dimethylphenyl)‐N‐methyl‐formamidine (BTS‐27271) were administered orally to white rats. Both compounds were rapidly metabolized and eliminated primarily via the urine. The cumulative percentage of the dose eliminated in the urine was 77.6 for amitraz and 88.7 for BTS‐27271 by 96 hr posttreatment. Amitraz degradation products present in urine included BTS‐27271, 2,4‐dimethylformanilide, 2,4‐dimethylaniline, 4‐formamido‐3‐methylbenzoic acid, 4‐amino‐3‐methylbenzoic acid, and several unknowns. BTS‐27271 degradation products in rat urine were similar to those found with amitraz. Tissue residues generally were low (<25 ppb) with the exception of those in liver.     

Detectability of phenoxy herbicides by chlorophyll fluorescence

Abstract

Trace amounts of 2,4‐D ‐ which does not cause visible damage in plant ‐ are detectable in plant leaves by chlorophyll fluorescence regeneration in two ways. (I) In illuminated leaves the level of first and second fluorescence peak differ in treated and untreated leaves. (2) By taking buffer solution (pH=8.6) in dark‐adapted leaves under vacuum, the first, second and the other fluorescence decrease levels differ in untreated and 2,4‐D or MCPA treated leaves.     

Genotoxicity of methyl parathion in short‐term bacterial test systems

Abstract

Genotoxicity of the insecticide methyl parathion was investigated in Salmonella typhimurium and Escherichia coli bacterial test systems for the detection of back mutations and DNA‐damage. Methyl parathion was mutagenic to S. typhimurium strain TA100 after activation with rat liver microsomal and cytosolic enzymes. In DNA repair tests, methyl parathion was effective in inducing damage to the S. typhimurium strain TA1538 which lack excision repair compared to the strain TA1978 which is proficient in excision repair mechanisms. Normal laboratory light conditions had no effect on the mutagenicity tests, however, exposure of methyl parathion in the petri dish containing the tester strain TA100 and rat liver microsomal and cytosolic enzymes reduced the mutagenic activity and increased the toxic effects of methyl parathion.     

Methylation mechanism of tin(II) by methylcobalamin in aquatic systems

The methylation reaction of tin(II) with methylcobalamin (CH(3)B(12)) in aquatic systems was modeled in the laboratory. The products were detected by a sensitive gas chromatography-flame photometric detector (GC-FPD), and further identified by gas chromatography-mass spectrometry (GC-MS). Both monomethyltin (MMT) and dimethyltin (DMT) were found as methylation products. Three important effecting factors during the methylation reaction, salinity, pH and aerobic or anaerobic, were studied. The results showed that methyl group can be transferred from CH(3)B(12) to tin in aquatic solutions as a radical or carbonium, as well as a carbanion. Two explanations for the pH-dependency of the methylation reaction between tin(II) and CH(3)B(12) were proposed: pH-dependency of the equilibrium states of CH(3)B(12), and pH-dependency of inorganic tin(II) species whose reactivity vary with the redox potential in the solution. Salinity can influence the activity of the methyl donor, which cause changes in the methylation efficiency. Kinetic experiments showed that the methylation reaction was pseudo-first-order for CH(3)B(12).     

Novel synthetic approach to the potent germination stimulant strigol and its analogues

Abstract

Strigol (1) is a natural product that triggers suicidal germination of parasitic Striga species. Here we present an improved annulation sequence for the synthesis of the tricyclic moieties of strigol and its analogues. Our approach makes use of the one‐pot cyclization of 5‐nitro‐2‐pentanone and cyclopent‐2‐enone diesters to afford 7‐methyl‐4‐nitro‐l‐oxo‐hydrindene derivatives. Functional group elaboration of these intermediates leads to a series of hydrindene‐2‐acetic and propionic acids.     

Evidence of degradation of polybrominated biphenyls in soil samples from michigan

Abstract

Soil samples obtained from the former polybrominated biphenyls (PBB) manufacturing site in Michigan were analyzed by gas chromatography and gas chromatography with mass spectrometric detection. The results indicate significant degradation of the PBB residue in the soil sample. The soil sample with the highest concentration of PBB has the greatest degree of degradation. Principal degradation products include 2,3’,4,4’,5‐pentabromo‐biphenyl, 2,2’,4,4’,5‐pencabromobiphenyl and two unidentified tetrabromobiphenyls.

The degradation pattern observed supports a photochemical decomposition mechanism. These degraded residues may be more toxic than the original Firemaster residues. The implications of the results are discussed.     

Azinphos Methyl Residues in Shallow Groundwater from the Fruit Production Region of Northern Patagonia,Argentina

Groundwater samples were collected from monitoring wells along an area of intensive fruit production. Different types of correlations were investigated between soil physicochemical characteristics, depths and agricultural practices with pesticide detection frequency. In the three analyzed periods azinphos methyl, S-(3,4-diydro-4-oxobenzo[d]-[1,2,3]-triazin-3-ylmethyl)-O,O-dimethyl phosphorodithioate, showed a definite seasonal behavior related to the application pattern, increasing its concentration in the aquifer from October to November-December and then decreasing towards March. Samples obtained during the non-spraying season showed that azinphos methyl residues were lower than detection limit (LOD).

An inverse correlation was observed between azinphos methyl concentration and the time elapsed since the last pesticide application. Seasonal events such as rain and irrigation influence the chemical concentration in the well, while no correlation was obtained between soil characteristics and azinphos methyl concentration. The soil attenuation capacity was not enough to prevent the presence of azinphos methyl in the aquifer during the application season.     

Induction of cytochrome p‐450 and phosphatidylcholine synthesis by endosulfan in liver of rats : Effect of quality of dietary proteins

Abstract

Administration of endosulfan significantly increased microsomal protein, cytochrome P‐450 content and the activity of aminopyrine N‐demethylase. Effect of endosulfan and actinomycin D either alone or together on microsomal protein, cytochrome P‐450, NADPH cytochrome c reductase, aniline hydroxylase, aminopyrine N‐demethylase, phosphatidylcholine content, incorporation of ³H‐choline and ¹⁴C‐methionine were studied in rats given amino acid deficient and supplemented diets. Administration of endosulfan significantly increased the above parameters in both the dietary groups, whereas administration of actinomycin D did not have any effect in rats fed supplemented diets, however, significant decrease in the PC and the incorporation of choline and methionine into PC of rats fed deficient diet were observed. A positive correlation in the effect of endosulfan on hepatic mixed function oxidase activity and hepatic phosphatidylcholine is observed.     

Human health effects of selected pesticides,chloroaniline derivatives.

Abstract

The health effects of two pesticides, chlordimeform and propanil, are discussed. Chlordimeform and 2‐methyl‐4‐chloroaniline, a major metabolite of chlordimeform, cause severe hemorrhagic cystitis in humans. In cats, however, only a mild effect on the bladder was noted. The herbicide propanil has produced chloracne in humans, and along with 3,4‐dichloroaniline, hyperkeratosis in rabbits. The contaminants 3,4,3’,4'‐tetrachloroazobenzene and 3,4,3’,4'‐tetrachloroazoxybenzene are responsible for the chloracnegenic characteristics of propanil, 3,4‐dichloroaniline, and methazole.     

Effects of metsulfuron‐methyl on microbial biomass and populations in soils

Abstract

Effects of the herbicide metsulfuron‐methyl on soil microorganisms and their activities in two soils were evaluated under laboratory conditions. Measurements included their populations, soil respiration, and microbial biomass. In the clay soil, bacterial populations decreased with increasing concentration of metsulfuron‐methyl during the first 9 days of incubation but exceeded that of the control soil from day 27 onward. In the sandy loam soil, the herbicide reduced bacterial populations during the first 3 days after application, but these increased to the level of untreated controls after 9 days’ incubation. Fungal populations in both soils increased with increasing metsulfuron‐methyl concentrations, especially in the sandy loam soil. CO₂ evolution was stimulated in both soils in the presence of the herbicide initially, but decreased during days 3 to 9 of the incubation period before increasing again afterward. The presence of metsulfuron‐methyl in the soil increased microbial biomass, except in sandy loam soil at the first day of incubation.     

Binding of aluminum to human serum transferrin,human serum albumin and rat serum proteins

Abstract

Human serum transferrin (HSTF), human serum albumin (HSA) and rat serum were compared for their interaction with AlCl₃ , in a Tris‐HCl buffer solutions (pH 7.4). The AlCl₃ was tested in series of concentrations in the range of 50 μM up to 500 μM . HSTF, HSA and their 1:1 mixture and rat serum were incubated at 37°C with series of AlCl₃ concentrations. The protein profile of the incubated solutions were compared to control using SDS‐PAGE and FPLC tests. The results indicated that HSTF was more specifically responsive to AlCl₃showing a characteristic increase in its UV absorption, peak and area dimensions. Simultaneously, HSA was less affected, but it showed a significant shift with an increase in molecular weight accompanied with a change in its profile. The respective bands of transferrin and albumin in rat serum behaved similarly. The SDS‐PAGE and FPLC data coincided and confirmed the preferential affinity of HSTF to bind with Al³⁺ . These results support the suggestion of using HSTF for monitoring levels of Al³⁺ in human blood samples of exposed population. The importance of further developing such a biomarker is the increased demand for early detection of the hazardous levels of Al³⁺ in relation to its long term neurotoxic adverse effects.     

Investigation of metal ions binding of humic substances using fluorescence emission and synchronous‐scan spectroscopy

Abstract

The binding site interactions of IHSS humic substances, Suwannee River Humic Acid, Suwannee River Fulvic Acid, Nordic Fulvic Acid, and Aldrich Humic Acid with various metals ions and a herbicide, methyl viologen were investigated using fluorescence emission and synchronous‐scan spectroscopy. The metal ions used were, Fe(III), Cr(III), Cr(VI), Pb(II), Cu(II) and Ni(II). Stern‐Volmer constants, K_SV for these quenchers were determined at pH 4 and 8 using an ionic strength of 0.1M. For all four humic substances, and at both pH studied, Fe(III) was found to be the most efficient quencher. Quenching efficiency was found to be 3–10 times higher at pH 8. The bimolecular quenching rate constants were found to exceed the maximum considered for diffusion controlled interactions, and indicate that the fluorophore and quencher are in close physical association. Synchronous‐scan spectra were found to change with pH and provided useful information on binding site interactions between humic substances and these quenchers.     

Aerobic and anaerobic degradation of profluralin and trifluralin

Abstract

The degradation of profluralin [N‐(cyclopropylmethyl)‐α,α,α‐trifluoro‐2,6‐dinitro‐N‐propyl‐]p‐toluidine] and trifluralin (α,α,α‐trifluoro‐2,6‐dinitro‐N,N‐dipropyl‐p‐toluidine) was studied under aerobic and anaerobic soil conditions. Three soils (Goldsboro loamy sand, Cecil loamy sand, Drummer clay loam) were each treated with 1 ppmw herbicide; anaerobic conditions were maintained by flooding. Soil samples were extracted monthly and subjected to TLC analysis. No degradation was detected in sterile controls. Aerobic degradation of both herbicides was greatest in the Cecil loamy sand soil over the entire incubation period. Degradation of profluralin in Cecil soil under aerobic conditions was 86 percent after 4 months with three products detected; 83 percent of the trifluralin was degraded with two products detected. Anaerobic degradation accounted for 72 percent of the profluralin and 78 percent of the trifluralin after 4 months. Degradation of both herbicides increased with incubation time for the first 3 months and decreased slightly thereafter. Generally there was more extensive degradation (percent and in number of products formed) of profluralin than trifluralin under the conditions tested. More degradation products were detected for both herbicides under aerobic conditions than under anaerobic conditions.     

Persistence of metsulfuron‐methyl in two soils

Abstract

The persistence of metsulfuron‐methyl in sandy loam and clay soil incubated at different temperatures and moistures contents was investigated under laboratory conditions using longbean (Vigna sesquipedalis L.) as bioassay species. A significant degradation of metsulfuron‐methyl was observed in non‐autoclaved soil rather than the autoclaved soil sample. At higher temperature, the degradation rate in non‐autoclaved soil improved with increasing soil moisture content. In non‐autoclaved sandy loam and clay soil, the half‐life was reduced from 9.0 to 5.7 and from 11.2 to 4.6 days, respectively when moisture level of sandy loam increased from 20 to 80% field capacity at 35°C. In the autoclaved soil, herbicide residue seems to have been broken down by non‐biological process. The rate of dissipation was slightly increased after the second application of the herbicide to non‐autoclaved soils but not in autoclaved soil, indicating the importance of microorganisms in the breakdown process.     

Pesticide concentration variations correlated with well bore volume removal in shallow coastal plain ground water

Abstract

The effects of well bore volume removal (V_n) on the concentration of alachlor [2‐chloro‐N‐(2,6‐diethylphenyl)‐N‐(methoxy methyl) acetamide] and prometon (6‐methoxy‐N,N'‐bis(1‐methylethyl)‐1,3,5‐triazine‐2,4‐diamine] in ground water obtained from three monitoring wells installed in the Coastal Plain region of North Carolina was investigated. Seasonal effects were also investigated by conducting the exercise in February and May. In the majority of cases, the lowest pesticide concentrations occurred in the initial well bore volume (V₁ = stagnant water). Removal of additional well bore volumes (V₂ to V₁₀) from two of the wells resulted in pesticide concentrations that did not vary substantially. This indicates that a representative aquifer sample was obtainable, in most cases from these wells, after removal of the initial well bore volume. In contrast, a third well required the purging of two well bore volumes before a stable alachlor concentration was achieved. Seasonal effects of bore volume removal vs. pesticide concentrations for the three wells were not significant (P > 0.05). It was concluded that a protocol for improved accuracy in pesticide analyses of ground water can be obtained by establishing a pesticide concentration‐purging (well bore volume) relationship for each well.