Reaktion von Pendimethalin in Lösung bei UV-bestrahlung

Pendimethalin (I) decomposed in hexane, methanol and aqueous methanol upon irradiation with UV-light (λ > 290 nm) to form “polar” products. The main products formed are the dinitroaniline (II) and the isomers mono-nitroanilines (III). Kinetic studies indicate that the photodegradation of pendimethalin is strongly dependent of solvent and concentration.     

Determination of pendimethalin (PROWL®480 EC) spray drift from ground applications

Abstract

Pendimethalin herbicide (PROWL^®480 EC) spray drift was determined from ground applications representing the highest rate applied to corn in eastern Canada. A novel drift collector pattern was laid out on the ground immediately before herbicide application. Most of the drift collectors were located downwind of the application target area. The maximum labelled rate of 1.68 kg ai/Ha was applied on 2 occasions on separate sites. In both applications, drift collector cards indicated that concentrations of pendimethalin were not detectable outside the target zone (<0.01 μg/cm²) at or beyond the 10 metre drift collector stations. Risk assessment calculations indicated that non‐target organisms would not be at significant risk from off‐site movement of pendimethalin.     

Dissipation of pendimethalin in the soil of field pea (Pisum sativum L.) and detection of terminal residues in plants

Dissipation of pendimethalin in the soil of field peas (Pisum sativum L.) at 0 to 110 days, and terminal residues in green and mature pea were studied under field conditions. Pendimethalin was applied as pre-emergence herbicide at 750, to 185 g a.i. ha^?1 in winter, in field peas. Dissipation of pendimethalin in the soil at 0 to 110 days followed first-order kinetics showing a half-life of 19.83 days averaged over all doses. Low pendimethalin residues were found in mature pea grain (0.004, 0.003, <0.001 μg g^?1), and straw (0.007, 0.002, <0.001 μg g^?1) at 750, 350 and 185 g a.i. ha^?1 treatments, respectively. The study indicated that residues of pendimethalin in green and mature pea were within the prescribed MRL limits.     

Effect of green manure amendment on herbicide pendimethalin on soil

Manure amendment in agricultural practice can have a large effect on herbicide dissipation because the period of manure plowing is close to the period of herbicide application. In addition, manure amendment is among the frequently encountered options in ameliorating pesticide pollution. In this research, the dissipation of the herbicide pendimethalin was examined after amendment with two common green manures, Lupinus luteus (L) or Cosmos bipinnatus (C), for 110 days in pH 5.2 and 7.7 soils (Sankengtzu [Sk] and Erhlin [Eh] soil, respectively). The microbial activity and ecology changes were examined by using Biolog EcoPlate and denaturing gradient gel electrophoresis (DGGE). In Sk soil, the half-lives of pendimethalin with L, C, and blank treatment were 49.0, 54.9, and 62.2 days, respectively, whereas that in Eh soil they were 46.3, 52.6, and 34.8 days, respectively. Pendimethalin dissipated quickly in more neutral soil (Eh soil), but the addition of manure can only increase the dissipation rate in acidic soil (Sk soil), indicating that the amendment of manures exerted different effect in pendimethalin dissipation rates in different pH soils. The application of pendimethalin and/or manure altered the microbial community activity after 24 h of incubation. After 110 days, the microbial community activities in green manure–amended soil were more similar to that with blank than pendimethalin treatment in both types of soils. In comparison with treatment C, microbial communities were more similar between treatment L and blank, indicating the superior effect over pendimethalin on microbial communities when applying Lupinus luteus. The research showed that the application of herbicide pendimethalin changed soil microbial community, and the amendment of manures exerted different effect in pendimethalin dissipation rates in different pH soils. It is assumed that the change in dissipation rates was originated from the microbial community change after different manure amendment.     

Effects of herbicide stress on wheat cultivars from organic and conventional cropping systems

Abstract

Wheat (Triticum aestivum L.) seedlings grown from seeds produced in “organic”; (non‐chemical) and “conventional”; cropping systems are characterized by a) similar rates of root and shoot growth, b) equal sensitivity to phytotoxicity by the herbicide glyphosate, and c) equivalent basal activity of the enzyme glutathione S‐transferase (both in the roots and in the shoots). In addition, treatment of these seedlings with glyphosate leads to significantly higher contents of this enzyme both in the shoots and in the roots. However, time‐course and dose‐response investigations indicate significant differences in the induction pattern of glutathione S‐transferase: the response of “conventional”; wheat seedlings takes place earlier and with higher efficiency, than that of the “organic”; ones.     

Dissipation of DDT in natural water under field conditions

Abstract

¹⁴C‐DDT dissipated gradually from natural water under outdoor conditions and declined to 40% of the applied radioactivity after 5 months. The losses are due to adsorption to particulates and volatilization from the water surface. In natural water DDT undergoes gradual conversion to DDE as the major degradation product and to a lesser extent to DDD. It may be concluded that DDT dissipates and degrades fairly rapidly in subtropical natural waters. Adsorption to particulate matter contributes to partial “removal” of DDT.     

Adsorption behavior of RH‐5992 insecticide onto sandy and clay loam forest soils

Abstract

Adsorption‐desorption behavior of RH‐5992 [Mimic®, N'‐t‐butyl‐N'‐(3,5‐dimethylbenzoyl)‐N‐(4‐ethylbenzoyl) hydrazine] in sandy and clay loam forest soils was studied using the batch equilibrium method. Adsorption was higher in the clay loam soil than in the sandy loam, and increased linearly with RH‐5992 concentration, but decreased with increasing pH and temperature. The adsorption data fit better to the Freundlich, than to the Langmuir equation. The K_D (linear adsorption constant) and K_F (Freundlich constant) were similar for each soil at 5, 15 and 25°C and decreased with increase of temperature, indicating that the enthalpy of adsorption was negative. The exponent of the Freundlich equation was close to unity for both soils at all three temperatures. The low E_a (energy of activation) indicated a diffusion‐controlled process during the initial stages of adsorption. The desorption isotherm differed from that of adsorption, and the linear desorption constant, K_D(d), was ca 25 times higher than the K_D, indicating that adsorption of RH‐5992 was not readily reversible. Evaluation of thermo‐dynamic parameters confirmed the presence of strong bonds between the solute and soil. These findings suggest that RH‐5992 has a limited potential for downward mobility leading to groundwater contamination.     

Fate of anilide and aniline herbicides in plant-materials-amended soils

The fate of herbicides trifluralin, pendimethalin, alachlor and metolachlor in paddy field soils amended with plant materials was investigated. The plant materials were purple sesbania, vegetable soybean and rice straw. The investigation was performed at two temperatures (25 and 40°C) and two soil water moistures (60 and 90% water-holding capacity). The results showed linear and Freudlich equations described the adsorption of amide compound to soil. Adsorption coefficient (K _d ) fit to linear equation were in general greater in plant material-amended soils than in non-amended soil, especially in soil amending with rice straw. Increasing temperature and soil water moisture content shortened the half-lives of compounds in various treated soils. The movement of compounds in the soil columns showed the maximum distribution of aniline type compound, trifluralin and pendimethalin, appeared at the upper top of 0 to 5 and 0 to 10 cm of soil column, respectively, and of anilide type, alachlor and metolachlor, were distributed at 0 to 25 cm of the soil column. The mobility of chemicals in the different treated soils was simulated by the behavior assessment model (BAM). There was no significant difference among different plant material incubated soils on dissipation and mobility of compounds in soils.     

Pendimethalin and oxyfluorfen degradation under two irrigation conditions over four years application

A four-year field study was conducted to determine the effect of pluviometric conditions on pendimethalin and oxyfluorfen soil dynamics. Adsorption, dissipation and soil movement were studied in a sandy loam soil from 2003 to 2007. Pendimethalin and oxyfluorfen were applied every year on August at 1.33 and 0.75 kg ha^?1, respectively. Herbicide soil concentrations were determined at 0, 10, 20, 40, 90 and 340 days after application (DAA), under two pluviometric regimens, natural rainfall and irrigated (30 mm every 15 days during the first 90 DAA). More than 74% of the herbicide applied was detected at the top 2.5 cm layer for both herbicides, and none was detected at 10 cm or deeper. Pendimethalin soil half-life ranged from 10.5 to 31.5 days, and was affected mainly by the time interval between application and the first rain event. Pendimethalin soil residues at 90 DAA fluctuated from 2.5 to 13.8% of the initial amount applied, and it decreased to 2.4 and 8.6% at 340 DAA. Oxyfluorfen was more persistent than pendimethalin as indicated by its soil half-life which ranged from 34.3 to 52.3 days, affected primarily by the rain amount at the first rainfall after application. Oxyfluorfen soil residues at 90 DAA ranged from 16.7 to 34.8% and it decreased to 3.3 and 17.9% at 340 DAA. Based on half-life values, herbicide soil residues after one year, and soil depth reached by the herbicides, we conclude that both herbicides should be considered as low risk to contaminate groundwater. However, herbicide concentration at the top 2.5 cm layer should be considered in cases where runoff or soil erosion could occur, because of the potential for surface water contamination.     

The metabolic fate of 14C‐parathion by some fresh water phytoplankton and its possible effects on the algal metabolism

Abstract

The growth and total carbohydrate contents of Nostoc muscorum and Tolypothrix tenuis were greatly and significantly reduced by the application of parathion. “Chlorophyll a”, carotene biosynthesis and the rate of glucose absorption were enhanced after supplementation of parathion to the culture media of both cyanobacteria. Nitrogen released to the media, total nitrogen content and total nitrogen fixed were increased in both organisms‐ Increase in protein content was accompanied by remarkable drop in amino, peptide and ammonia fractions‐ Phosphorus uptake, RNA, DNA and total phosphorus content were accelerated to reach maximum accumulation at the highest insecticide level. In metabolism study using ¹⁴C‐labelled compound, parathion was readily degraded by Nostoc and Tolypothrix. Following ten days incubation, the aqueous fractions contained 21.1% and 18.1% of the initial activity in Nostoc and Tolypothrix respectively. TLC analysis of the hydrolytic products revealed the presence of three metabolites: p‐aminophenol, p‐nitrophenol and aminoparathion.     

Removal of pesticides from rinsate by adsorption using agricultural residuals as medium

Abstract

The feasibility of using agricultural residual with highly organic matter content ‐ spent mushroom compost (SMC) as adsorption medium for removal of pesticides including carbaryl, carbofuran, and aldicarb with a concentration range of 0–30 mg/L from rinsate was investigated. Bottle‐point method was used to determine adsorption isotherms for single‐pesticide and multi‐pesticides. It was found that SMC might potentially be used for on‐farm treatment of pesticide rinsate. The adsorption capacity of SMC was increased compared to most soils, possibly related to the increased organic matter content. The rapid equilibrium of pesticide solution and SMC was consistent with a physical type of adsorption mechanism. The adsorption of carbamate pesticides on SMC was found to exhibit nonlinear “favorable”; adsorption behavior that could be characterized well by the Freundlich isotherm model. In addition, the multi‐pesticide adsorption tests displayed the characteristics of competitive behavior. The competitive ability of these three pesticides in multi‐components adsorption was in the order carbaryl > carbofuran > aldicarb, which was consistent with the adsorbability of pesticides.     

In vitro study of oxytetracycline adsorption on activated charcoal

Abstract

In vitro adsorption experiments simulating pH in gastric environment and using Langmuir isotherm, showed that 408 mg of oxytetracycline was adsorbed per gram of activated charcoal. Langmuir isotherm fitted adsorption data better than a Freundlich isotherm. Freundlich isotherm showed a specific adsorption capacity of 518 mg/g for activated charcoal. Both isotherm parameters indicated a strong oxytetracycline adsorption on activated charcoal in terms of quantity and binding strength. The results demonstrate that the concomitant use of oxytetracyline and activated charcoal should be avoided.     

Paraquat Adsorption,Degradation, and Remobilization in Tropical Soils of Thailand

Paraquat adsorption, degradation, and remobilization were investigated in representative tropical soils of Yom River Basin, Thailand. Adsorption of paraquat in eight soil samples using batch equilibration techniques indicated that adsorption depended on soil characteristics, including exchangeable basic cations and iron content. Multiple regression analysis indicated significant contribution of exchangeable calcium percentage (ECP), total iron content (TFe) and exchangeable sodium percentage (ESP) to paraquat sorption (Q). ESP and TFe were significant at all adsorption stages, whereas ESP was significant only at the initial stage of paraquat adsorption. Adsorption studies using two soils representing clay and sandy loam textures showed that paraquat adsorption followed the Freundlich model, exhibiting a nonlinear sorption curve. Paraquat adsorption was higher in the clay soil compared to the sandy loam soil with K _f values of 787 and 18, respectively. Desorption was low with 0.04 to 0.17% and 0.80 to 5.83% desorbed in clay and sandy loam soil, respectively, indicating some hysteresis effect. Time-dependent paraquat adsorption fitted to the Elovich kinetic model indicated that diffusion was a rate-limiting process. Paraquat mobility and degradation studies conducted using both field and laboratory soil column experiments with clay soil showed low mobility of paraquat with accumulation only in the surface 0–5 cm layer under field conditions and in the 0–1 cm layer in a laboratory soil column experiment. Degradation of paraquat in soil was faster under field conditions than at ambient laboratory conditions. The degradation rate followed a first-order kinetic model with the DT₅₀ at 36–46 days and DT₉₀ around 119–152 days.     

Teratogenicity of bifenox and nitrofen in rodents

Abstract

The teratogenicity of the diphenyl ether herbicide bifenox [2,4‐dichlorophenyl 3'‐carboxymethyl‐4'‐nitrophenyl ether] was compared to that of nitrofen [2,4‐dichlorophenyl 4'‐nitrophenyl ether] in rats and in mice. Neither compound increased prenatal mortality in mice. Because nitrofen causes both malformations that are compatible with survival to weaning and a high incidence of perinatal (but not of fetal) mortality, emphasis was placed on postnatal parameters of bifenox toxicity. In rats, bifenox caused a low incidence of “bloody tears”;, but it did not decrease survival to term or to weaning in rats or mice, and did not reduce Harderian gland weight in mice. Because the weight of the Harderian glands is a more objective measure of their status than is the presence of an eye discharge, it is concluded that bifenox is not teratogenic at the levels administered. Nitrofen decreased litter size, pup weight, and Harderian gland weight in mice.     

Attractancy evaluation of ceralure‐B1 isomer via field captures of mediterranean fruit flies (Diptera: Tephritidae)

Abstract

Commercially prepared ceralure‐B1, an attractant for the Mediterranean fruit fly, Ceratitis capitata (Wiedemann) (Diptera: Tephritidae), was evaluated in trapping tests by comparison with commercial ceralure and trimedlure. Jackson traps were used for medfly captures. The residual ceralure‐B1, ceralure, and trimedlure contents of aged dispensers were determined. The results of this study show that male medfly captures from traps with ceralure‐B1 were as high or higher than male medfly captures from traps with twice the quantity of ceralure or trimedlure. The use of regioselectively synthesized ceralure‐B1, enriched in B1, as a source of a more potent attractant than commercial ceralure and as a more persistent male medfly attractant than trimedlure is reported.     

A Reexamination of the Ozone Limiting Approach to Estimating Short-Term NO2 Concentrations

The partition and effective diffusion coefficients of formaldehyde were measured for three materials (conventional gypsum wallboard, “green” gypsum wallboard, and “green” carpet) under three relative humidity (RH) conditions (20%, 50%, and 70% RH). The “green” materials contained recycled materials and were friendly to environment. A dynamic dual-chamber test method was used. Results showed that a higher relative humidity led to a larger effective diffusion coefficient for two kinds of wallboards and carpet. The carpet was also found to be very permeable resulting in an effective diffusion coefficient at the same order of magnitude with the formaldehyde diffusion coefficient in air. The partition coefficient (K _ma) of formaldehyde in conventional wallboard was 1.52 times larger at 50% RH than at 20% RH, whereas it decreased slightly from 50% to 70% RH, presumably due to the combined effects of water solubility of formaldehyde and micro-pore blocking by condensed moisture at the high RH level. The partition coefficient of formaldehyde increased slightly with the increase of relative humidity in “green” wallboard and “green” carpet. At the same relative humidity level, the “green” wallboard had larger partition coefficient and effective diffusion coefficient than the conventional wallboard, presumably due to the micro-pore structure differences between the two materials. The data generated could be used to assess the sorption effects of formaldehyde on building materials and to evaluate its impact on the formaldehyde concentration in buildings.

Implications: Based on the results of this study, the sink effects of these commonly used materials (conventional and “green” gypsum wallboards, “green” carpet) on indoor formaldehyde concentration could be estimated. The effects of relative humidity on the diffusion and partition coefficients of formaldehyde were found to differ for materials and for different humidity levels, indicating the need for further investigation of the mechanisms through which humidity effects take place.     

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.     

Colloid‐facilitated transport of metolachlor through intact soil columns

Abstract

This study evaluated the role of water dispersible colloids with diverse physicochemical and mineralogical characteristics in facilitating the transport of metolachlor through macropores of intact soil columns. The soil columns represented upper solum horizons of an Alfisol in the Bluegrass region of Kentucky. Three different colloid suspensions tagged with metolachlor [2‐chloro‐N‐(2‐ethyl‐6‐methylphenyl)‐N‐(2‐methoxy‐l‐methylethyl)acetamide] were introduced at a constant flux into undisturbed soil columns. The eluents were collected and analyzed periodically for colloid and metolachlor concentrations. Colloid recovery in the eluents ranged from 54 to 90 %. The presence of colloids enhanced the transport of metolachlor by 22 to 70 % depending on the colloid type and mobility. Colloids with higher pH, organic carbon, cation exchange capacity (CEC), total exchangeable bases (TEB), surface area (SA), and electrophoretic mobility (EM), showed better mobility, greater affinity for interaction with the herbicide and, thus, greater potential to co‐transport metolachlor. In contrast, increased level of kaolinite, Fe, and Al inhibited metolachlor adsorption and transport. In spite of the increased transportability of metolachlor by the presence of soil colloids, the colloid bound herbicide portion accounted for a very small part of the observed increase. This suggests that surface site exclusion mechanisms and preferential sorption induced by the presence of colloids are more important than ion exchange phenomena in promoting herbicide mobility in subsurface environments.     

Removal of anionic azo dye from aqueous solution via an adsorption–photosensitized regeneration process on a TiO2 surface

Textile dye effluents are typically characterized by strong color and recalcitrance, even at very low concentration. The process of enrichment of anionic azo dye on the surface of TiO₂ fibers followed by photosensitization degradation under ambient air conditions was extensively investigated. Adsorption isotherms and zeta potentials were used to describe the “dye/TiO₂ surface” interface, taking into account the effects of pH on the nature and population of the surface groups on the TiO₂ fibers. The extent of the photocatalytic degradation of dye on TiO₂ surface was determined by FTIR. N₂ adsorption isotherms and optical spectra were employed to investigate the effect of photosensitization. The adsorption of dyes on the TiO₂ surface occurs via electrostatic attraction through the formation of single- or multidentate-coordinated surface complexes. Almost complete photobleaching of the absorption band at 534 nm is achieved in ~4 h. Dye-sensitized TiO₂ fiber could absorb part of the visible light spectrum (λ?<?600 nm). Interfacial electron transfer can potentially alter the degradation efficiency. The regenerated TiO₂ fiber could be reused for subsequent decolorization without a decline in adsorption efficiency compared with freshly prepared TiO₂ samples, which may be attributed to preservation of the hierarchical pore structure and restoration of the original surface properties. In summary, we propose an efficient “adsorption–photoregeneration–reuse” process applying TiO₂ fibers for the degradation of dyes in water.     

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.