Sorption and leaching potential of herbicides on Brazilian soils

Sorption of the herbicides alachlor, atrazine, dicamba, hexazinone, imazethapyr, metsulfuron-methyl, nicosulfuron, simazine and sulfometuron-methyl was characterized on six Brazilian soils, using the batch equilibration method. In general, weak acid herbicides (dicamba, imazethapyr, metsulfuron-methyl, nicosulfuron and sulfometuron-methyl) were the least sorbed, whereas weak bases such as triazines and nonionic herbicides (alachlor) were the most sorbed. The Kd values found showed a significant correlation with soil organic carbon content (OC) for all herbicides except imazethapyr and nicosulfuron. Koc values showed a smaller variation among soils than Kd . To estimate the leaching potential, Koc and the ground-water ubiquity score (GUS) were used to calculate half-lives ( t_1/2 ) that would rank these herbicides as leachers or non-leachers. Comparison of calculated values to published values for t_1/2 demonstrated that sulfonylureas and hexazinone are leachers in all soils, alachlor is transitional, and atrazine, simazine and dicamba are leachers or transitional, depending on soil type. Results discussed in this paper provide background to prioritize herbicides or chemical groups that should be evaluated in field conditions with regard to their leaching potential to ground-water in tropical soils.     

Degradation and sorption of atrazine, hexazinone and procymidone in coastal sand aquifer media

The degradation, sorption and transport of atrazine, hexazinone and procymidone in saturated coastal sand aquifer media were investigated in batch and column experiments. The pesticides were incubated with sterilised and non-sterilised groundwater or a mixture of groundwater and the aquifer material in the dark at 15 degrees C for 120 days. The estimated half-lives of the pesticides (and their ranges) in the mixture of groundwater and aquifer sand were 36 (31-40), 54 (40-77) and 84 (46-260) days for atrazine, procymidone and hexazinone, respectively. Compared with the relevant results for the groundwater-sand mixture phase, the estimated half-life of pesticides in the groundwater phase alone was shorter for procymidone (21 days) but longer for hexazinone (134 days); atrazine was not degraded in the groundwater phase. Chemical degradation appeared to have played the predominant role in the degradation of hexazinone and procymidone in the aquifer system, while both chemical and biological processes seemed to be important for the degradation of atrazine. Batch isothermal experiments were carried out at pH 4.6-4.7 to obtain sorption coefficients under equilibrium conditions. The isothermal data of the pesticides fitted well with the non-linear Freundlich function with an exponent of sorption coefficient that was greater than one. Contrary to reports in the literature, sorption of atrazine was the greatest, and procymidone was slightly more sorbed than hexazinone. A column experiment was conducted at a typical field-flow velocity of 0.5 m day(-1) over 60 days to study pesticide attenuation and transport in flow dynamic conditions. Retardation factors, R, derived from a two-site sorption/desorption model were 8.22, 1.76 and 1.63 for atrazine, procymidone and hexazinone, respectively. Atrazine displayed the lowest mobility and the mobility of procymidone was only slightly less than that of hexazinone, which is consistent with observations in the batch experiment. A possible explanation for these observations is that ionic atrazine is bound to oppositely charged ionic oxides, and ionic oxides have less effect on the sorption of the non-ionic procymidone. The significant tailing in the pesticide breakthrough curves (BTCs) in comparison with the bromide BTC, together with model-simulated results, suggests that the transport of the pesticides was under chemical non-equilibrium conditions with R values that were less than their equivalent values predicted using the batch equilibrium isothermal data. As a result of non-linear kinetic sorption, retardation factors of the pesticides in groundwater systems would not be constant and will decrease with decreasing pesticide concentrations and increasing flow velocities. Hence, the use of equilibrium isotherm data will probably over-predict the sorption of pesticides in groundwater systems. Rhodamine WT, a commonly used groundwater tracer, was significantly retarded (R = 5.48) and its BTC was much more spread out than the bromide BTC. Therefore, it would not be a good tracer for the indication of groundwater flow velocity and dispersion for the coastal sand aquifer system. In contrast to some aquifer media, the dye tracer was unsuitable as a marker of the appearance of atrazine in a coastal sand aquifer system.     

Chemical hydrolysis of 2-chloro-4,6-bis(alkylamino)-1,3,5-triazine herbicides and their breakdown in soil under the influence of adsorption

The determination of rate constants and the calculation of the activation parameters [activation energy (E_a), free energy of activation(ΔG^≠)and entropy of activation (ΔS^≠)] demonstrated the identity of the reaction kinetics of chemical hydrolysis of the chlorinated triazine herbicides simazine, atrazine, propazine and terbuthylazine. Persistence in soil could be estimated, from the hydrolytic half-life time, only in pH regions where these compounds were also sensitive to chemical hydrolysis. In general, the rate of hydrolysis increased in the presence of soil as the result of a catalysing effect of the soil in their breakdown. When half-lives in soil of these triazine herbicides were compared with adsorption constants, a functional relationship was observed in both soil types; as adsorption increased the half-life in soil also increased.     

Evidence for cross-adaptation between s-triazine herbicides resulting in reduced efficacy under field conditions

BACKGROUND: Enhanced atrazine degradation has been observed in agricultural soils from around the globe. Soils exhibiting enhanced atrazine degradation may be cross-adapted with other s-triazine herbicides, thereby reducing their control of sensitive weed species. The aims of this study were (1) to determine the field persistence of simazine in atrazine-adapted and non-adapted soils, (2) to compare mineralization of ring-labeled (14)C-simazine and (14)C-atrazine between atrazine-adapted and non-adapted soils and (3) to evaluate prickly sida control with simazine in atrazine-adapted and non-adapted soils.RESULTS: Pooled over two pre-emergent (PRE) application dates, simazine field persistence was 1.4-fold lower in atrazine-adapted than in non-adapted soils. For both simazine and atrazine, the mineralization lag phase was 4.3-fold shorter and the mineralization rate constant was 3.5-fold higher in atrazine-adapted than in non-adapted soils. Collectively, the persistence and mineralization data confirm cross-adaptation between these s-triazine herbicides. In non-adapted soils, simazine PRE at the 15 March and 17 April planting dates reduced prickly sida density at least 5.4-fold compared with the no simazine PRE treatment. Conversely, in atrazine-adapted soils, prickly sida densities were not statistically different between simazine PRE and no simazine PRE at either planting date, thereby indicating reduced simazine efficacy in atrazine-adapted soils.CONCLUSIONS: Results demonstrate the potential for cross-adaptation among s-triazine herbicides and the subsequent reduction in the control of otherwise sensitive weed species. Copyright (c) 2008 Society of Chemical Industry.     

Residualwirkung von Chlortriazin-Herbiziden im Boden an drei rumänischen Standorten. I. Prognose der Persistenz von Simazin und Atrazin im Boden

Residual effects of chlorotriazine herbicides in soil at three Rumanian sites. I. Prediction of the persistence of simazine and atrazine Persistence of simazine and atrazine in the top 10 cm soil was measured at three sites in Rumania with variations in climate and soil conditions. Both herbicides were applied at 1 and 3 kg ai ha^?1 to uncropped plots and to plots cropped with maize (Zea mays L.). Rates of residue decline were independent of application rate and crop cover but varied between sites. The time for 50% loss of atrazine varied from 36 to 68 days and that of simazine from 48 to 70 days. Laboratory studies were made with atrazine to characterize degradation rates under standard conditions and to measure adsorption and leaching behaviour in the different soils. Weather records for the periods of the field experiments were used in conjunction with appropriate constants derived from the laboratory results, or from data in the literature, in a computer program to simulate persistence in the field. Results from the model were in reasonable agreement with the observed soil residues although there was a tendency to overestimate rates of loss on some occasions. The results suggest that the model of persistence was sufficiently accurate for practical purposes, and that its use could preclude the need for extensive analytical measurements of residues.     

Simulation of herbicide persistence in soil .II. Simazine and linuron in long-term experiments

The rates of degradation of simazine and linuron were measured in soil from plots not treated previously with these herbicides. Degradation of both compounds followed first-order kinetics and soil temperature and soil moisture content had a marked effect on the rate of loss. With linuron, half-lives increased from 36 to 106 days with a reduction in temperature from 30° to 5°C at 4% soil moisture, and from 29 to 83 days at 12% soil moisture. Similar temperature changes increased the half-life of simazine from 29 to 209 days and from 16 to 125 days at soil moisture contents of 4 and 12% respectively. A computer program which has been developed for simulation of herbicide persistence was used in conjunction with the laboratory data and the relevant meteorological records for the years 1964 to 1968 in order to test the model against previously published field persistence data for the two herbicides. The results with simazine showed a close correspondence between observed and predicted residue levels but those for linuron, particularly in uncropped plots, were satisfactory for limited periods only.     

Bioefficacy and leaching of controlled-release formulations of triazine herbicides

Conventional formulations of atrazine and simazine were compared with controlled-release formulations of these two herbicides for bioefficacy, leaching and crop safety in laboratory and field experiments. Three light-textured soils with a pH range of 5.8–8.5 were used for this work. An oat bioassay (Avena sativa L.) was used to quantify soil concentrations of the herbicides. Comparison of the initial bioefficacy of controlled-release formulations of atrazine and simazine showed their respective relative potencies to conventional formulations to be 0.51–0.85. The results indicated that the controlled-release formulations maintained an entrapped reserve of active ingredient after delivery with a conventional boomsprayer. In laboratory trials, the controlled-release formulations showed a reduction in leaching compared with conventional formulations. A controlled-release formulation and a conventional formulation of atrazine were tested further in a field trial. A higher concentration of atrazine in topsoil from the controlled-release formulation was observed 11 weeks after application after 107 mm of rainfall. It was deduced that this was caused by reduced leaching of the controlled-release formulation, as observed in laboratory trials. EWRC scores for the control of a range of grass and broad-leaved weeds were identical for both formulations. This indicated that, while the controlled-release formulation could inhibit leaching of the active ingredient, it did not hinder the level of potency necessary for early weed control. EWRC crop safety ratings of chickpeas (Cicer arietinum L.) sown at application were higher for the controlled-release formulation 10 weeks after sowing, and subsequent harvest yields were 50% higher. It was inferred that this resulted from a favourable interaction between crop growth and the timing of the release of the active ingredient from the controlled-release formulation. Altogether, the controlled-release formulations displayed the necessary prerequisites for their further development for large-scale use under arable regimes.     

Rapid dissipation of atrazine in soils taken from various maize fields

A laboratory study was carried out in order to measure the degradation rate of atrazine in 36 different soils taken from maize ( Zea mays L.) fields in Belgium. These soils differed in their alrazme treatment histories. pH. organic matter content and type of organic and mineral fertili-zation, Half-lives of less than 10 days were found in more than 60% of the soils sampled. This rapid dissipation could be linked in a significant way to repeated pretreaiments with atrazine (intensive maize cropping) as well as to higher pH values (from neutral to alkaline), A low organic matter content might also be a factor explaining the rapid degradation of atrazine. but to a lesser extent than the first two factors. On the other hand mineral fertilization was shown to slow down atrazine dissipation. It is hypothesized that repeated treatments of atrazine cause a mi-crobial adaptation to atrazine degradation and that acidic soil conditions impede this adaptation. To date, this is the first time that evidence for widespread accelerated degradation of atrazine has been reported.     

TRIAZINE HERBICIDES ON MAIZE AND THEIR RESIDUAL EFFECTS ON FOLLOWING CROPS*

Summary. Pre-emergence application of 2–5 kg/ha (a.i.) of atrazine or simazine was the most effective treatment for control of broad-leaved weeds in maize. Other triazines injured maize at all rates tested. Among the crops following maize treated with atrazine or simazine at 2–5 kg/ha, sugar beet was injured whereas wheat, oats, vetch, onions and soybeans were not. Post-emergence application of triazine herbicides was not effective and did not increase maize yields significantly over those of the unweeded plots. Wheat, oats, vetch and sugar beet were injured when following maize treated with post-emergence sprays; onions and soybeans showed no visible injury except from atrazine or simazine at 5 kg/ha or more, and from mixtures of atrazine+prometryne or atrazine+ametryne at 12–5 kg/ha. Les triazines herbicides sur le mais et leurs arrière-effets sur les cultures suivantes     

Evaluation of herbicides for maize production in three ecological zones of Nigeria

Abstract

Maize cultivation in Nigeria has increased rapidly in the last few years as fertilizers have become more readily available to farmers. Without the use of herbicides however, the area of land that can be brought under maize production will be limited. The following herbicides were evaluated in three ecological zones of Nigeria: atrazine and mixtures of atrazine and simazine, atrazine and metolachlor and atrazine and cyanazine. All herbicide treatments were applied at the rate of either 1.0 or 2.0 kg a.i./ha. The plots that received 1.0 kg a.i./ha also received one supplementary hand weeding. All treatments gave yields comparable to the weed free control, with the exception of the unweeded higher rate of the atrazine and cyanazine treatment which gave the lowest grain yield as a result of poor weed control.     

Influence of Compost Addition to Soil on the Behaviour of Herbicides

The transformations of eight herbicides (atrazine, simazine, terbutryn, pendimethalin, carbetamide, 2,4-D, metsulfuron-methyl and dimefuron) in soil after compost addition were monitored during long-term laboratory incubations. The herbicides were applied to soil, compost and soil-compost mixtures. Herbicide sorption, their kinetics of mineralisation and the extractability of residues were compared in the different treatments. Compost addition to soil generally decreased herbicide mineralisation and favoured the stabilisation of herbicide residues. A fraction of the stabilised residues remained extractable and potentially available. However, most of them were unextractable and formed bound residues. Sorption could be at the origin of a kinetically limited biodegradation, mainly for the most highly-sorbed herbicides (atrazine, simazine, terbutryn, pendimethalin and dimefuron). Compost addition had little effects on the less sorbed herbicides (carbetamide, 2,4-D and metsulfuron- methyl). © 1997 SCI.     

Cinétique de dissolution dans l'eau de l'atrazine, de la propazine et de la simazine

The kinetics of dissolution of atrazine, propazine and simazine in water The solubaility and kinetics of solubilization of atrazine, propazine and simazine in water were studied at different temperatures. The apparent order of the dissolution reactions is 1 for atrazine and propazine and 2 for simazine. The solubility and rate constants are Increasing functions of the temperature. Activation energies of solubilization are of the order of 41 to 4–8 kcal/mole; they correspond to a 30% decrease in the time of a 50% solubilization when temperature increases by 10°C. It seems therefore that the effectiveness of a treatment can depend in part on the amount of rain and the soil temperature.     

ABSORPTION AND TRANSLOCATION OF HERBICIDES BY THOMPSON SEEDLESS (SULTANINA) CRAPE, VITIS VINIFERA L.

Summary. Absorption and translocation of ¹⁴C-labelled herbicides applied in culture solutions lo the roots and in concentrated drops to mature leaves of 'Thompson Seedless' (Sultanina) cuttings were studied. Neither 2,4-D nor paraquat, and only traces of 2,4,5-T translocated from the roots to the shoot. Dicamba, amitrole, diuron, monuron, simazine and atrazine readily moved from the roots to the shoots. The substituted ureas and s -triazines were mobile only in the xylem or cell walls (apoplast), while dicamba and amitrole were mobile in the apoplast and symplast (living protoplasm). Both 2,4-D and 2,4,5-T moved almost entirely in the symplast. Paraquat moved only slightly in either apoplast or symplast. Stability of the herbicides in the plants varied, as judged by the detection of label in ethanol-insoluble products. Dicamba was considerably more stable than 2,4,5-T which, in turn, was more stable than 2,4-D. Diuron was more stable than either atrazine or simazine. Amitrole largely was converted into ethanol-insoluble products in 30 days. Paraquat was not extractable with ethanol.
Absorption et migration d'herbicides chez une vigne: Thompson Seedless (Sultanina), Vitis vinifera L.     

Interactions between soil-applied herbicides in the roots of some legume species

The effects on plant growth of applying trifluralin or nitralin combination with simazine, atrazine, prometryne and linuron to the upper 5-cm root region of vetch (Vicia sativa L.), pea (Pisum sativum L.) and soybean (Glycine max) were investigated. Foliar injury due to herbicides of the second group was markedly reduced in each species by simultaneous treatment with trifluralin or nitralin both of which inhibited lateral root growth without affecting aerial plant growth or tap root extension growth. This inhibition of lateral root growth in roots treated with trifluralin or nitralin was associated with reduced uptake and subsequent transport to the foliage of ¹⁴C-labelled simazine in vetch and pea and ¹⁴C-labelled atrazine in soybean. This probably accounted for the reduction in simazine and atrazine phytotoxicity. In the presence of trifluralin or nitralin comparatively higher amounts of radioactivity were retained in the roots of pea and soybean and this reduced the amount of ¹⁴C available for transport to the foliage. This was not evident in vetch.     

SHOOT ZONE UPTAKE OF SOIL-APPLIED HERBICIDES IN PISUM SATIVUM L.

Summary. The effects of localized herbicide placement at different internodes of pea ( Pisum sativum L. cv. Alaska) shoots below the soil surface after plant emergence were studied by removing the soil from around the shoots and replacing with herbicide-treated soil. The first internode proved insensitive to linuron, diuron, atrazine and simazine at 4·5 kg/ha, while treatment of the second and third internodes markedly reduced plant growth 4–6 days after treatment. Separate exposure of the first internode alone, and the second and part of the third together to ¹⁴C-labelled atrazine indicated no difference in herbicide metabolism. However, a two- to threefold increase in ¹⁴C uptake and movement to the foliar parts occurred when the second and part of the third internode was treated, as compared to first internode treatment. Thus the differential sensitivity of the internodes to atrazine, and possibly to the other herbicides, may be because the more mature first internode allows less uptake and subsequent movement to the foliar parts.
Absorption dans la zone des tiges des herbicides appliqués dans le sol chez Pisum sativum L.     

表面活性剂辅助-凝固-漂浮分散液-液微萃取-高效液相色谱法检测葡萄酒中4种三嗪类除草剂残留

建立了表面活性剂辅助-凝固-漂浮分散液-液微萃取-高效液相色谱(SA-DLLME-SFO-HPLC)法检测葡萄酒中西玛津、莠去津、特丁津和扑草净4种三嗪类除草剂残留的分析方法。考察了萃取剂的类型、萃取剂和表面活性剂的体积、萃取时间和盐效应等对萃取效率的影响,确定最佳萃取条件为:20 μL十一醇作为萃取剂,2 μL 0.25 g/L的Tween-20水溶液作为分散剂,萃取时间10 min,氯化钠的质量浓度为250 g/L。结果表明:西玛津、莠去津、特丁津和扑草净的线性范围为0.008~5 mg/L,检出限分别为2.4、1.8、2.0和2.8 μg/L,富集倍数在24.5~32.4之间。在0.008、0.08和2.4 mg/L添加水平下,西玛津、莠去津、特丁津和扑草净在葡萄酒中的回收率在84%~102%之间,相对标准偏差(n=5)在2.1%~6.9%之间。该方法可用于葡萄酒中西玛津、莠去津、特丁津和扑草净残留量的测定。     

Transport to ground‐water of six commonly used herbicides: a prediction for two Italian scenarios

In Italy suitable standard scenarios for pesticide risk assessment based on computer models are lacking. In this paper we examine the use of the VARLEACH model to assess the potential danger of ground‐water pollution by six herbicides (alachlor, atrazine, cyanazine, linuron, simazine and terbuthylazine) which are used to protect irrigated (maize) and non‐irrigated (sorghum) crops in the Po Plain, one of the most important agricultural lands in Italy. Two extreme scenarios are taken: real worst case (sandy soil) and real best case (clay loam soil). The simulation suggests that cyanazine, linuron and terbuthylazine can be safely used in clay loam soil in both non‐irrigated and irrigated crops, while alachlor, atrazine and simazine can be safely used only in non‐irrigated crops. On the other hand, the application of all the herbicides tested should be avoided in sandy soil, with the exception of linuron in non‐irrigated crops. © 2000 Society of Chemical Industry     

Breakdown rates of dimethoate in fruit and vegetable dips

In order to determine the effect of pH and temperature on post-harvest dip solutions of dimethoate (500 mg litre^?1), the half-lives and pseudo first-order rate constants were calculated from measurements at pH 4, 6, 8, 10, 11.5, and at two temperatures 25 and 52°C. The half-lives ranged from 206 days to 39.3 min at 25°C, and from 5.6 days to 205s at 52°C; the rate constants ranged from 3.9 × 10^?8 s^?1 to 2.9 × 10^?4 s^?1 at 25°C, and from 1.4 × 10^?6 s^?1 to 3.4 × 10^?3 s^?1 at 52°C. The results show that the water used in dips should have a pH≤7. The addition of benomyl to the dip solutions at two concentrations (0.5 and 1.0 g litre^?1) had no effect on the half-lives and rate constants. The use of hard and salted waters in dips also showed no major effect. A formula was developed that gives the half-life of the dimethoate as a function of the pH and temperature.     

Uptake and translocation of some pesticides by hypocotyls of radish seedlings

Some of the factors affecting absorption and translocation of pesticides by the hypocotyls of intact radish (Raphanus sativus, L., cv. Black Spanish) seedlings have been studied, particular attention being given to the triazine herbicides simazine, atrazine and atraton. Uptake and translocation appear to be largely passive processes and by contrast with foliar absorption seem to be unaffected by humidity, con-centration, light and by the aqueous solubilities of the compounds. Diffusion across the tissues of the hypocotyl, rather than rate of transpiration, appears to determine the rate at which atrazine and simazine are translocated to the cotyledons. For several pesticides there is a qualitative relationship between the percentages of the compounds translocated to the upper portion of the shoots and their partition coefficients in oil/water systems. In conclusion, some consideration is given to the relative importance of uptake by roots and shoots under field conditions.     

Chemical management of weeds in corn hybrids

Corn stands out among the cultivars because of its high importance in food, animal feed and raw materials for energy production. The quantity and quality of the harvested grain can be reduced, mainly due to inadequate weed management. Nowadays, weed control is accomplished with the use of herbicides as pre‐emergence and postemergence, applied alone or in a tank mix. This study aimed to evaluate the efficiency of the control of weeds and phytotoxicity of the herbicides that were applied in tank mix or isolated in the corn hybrids, Formula TL® and SYN 7B28 . Two experiments were conducted: in the 2012/2013 season (Formula TL®) and 2013/2014 season (SYN 7B28). There was a low initial phytotoxicity of all the tested herbicides in the initial evaluation; however, from 14 days after treatment, it was minimal. The weed control of Ipomoea indivisa, Urochloa plantaginea and Euphorbia heterophylla in both experiments was better, in general, when using the tank mixtures of atrazine + simazine + tembotrione and atrazine + simazine + mesotrione, respectively. The application of atrazine + simazine + tembotrione in the SYN 7B28 hybrids provided, with the exception of the thousand‐grain weight, the best expression of grain yield components, combining a low phytotoxicity and best control of the weeds. The Formula TL® hybrid presented the highest mass of a thousand grains and yield with the application of nicosulfuron + tembotrione. The yield average difference of the herbicide treatments and the unweeded control showed an increase of 27.66 and 34.59% in the grain yield of the corn hybrids, Formula TL® and SYN 7B28, respectively.