Fate of the herbicide glyphosate and its metabolite AMPA in soils and their transfer to surface waters: A multi-scale approach in the Lavaux vineyards, western Switzerland

The use of herbicides in agriculture may lead to environmental problems, such as surface water pollution, with a potential risk for aquatic organisms. The herbicide glyphosate is the most used active ingredient in the world and in Switzerland. In the Lavaux vineyards it is nearly the only molecule applied. This work aimed at studying its fate in soils and its transfer to surface waters, using a multi-scale approach: from molecular (10-9 m) and microscopic scales (10-6 m), to macroscopic (m) and landscape ones (103 m). First of all, an analytical method was developed for the trace level quantification of this widely used herbicide and its main by-product, aminomethylphosphonic acid (AMPA). Due to their polar nature, their derivatization with 9-fluorenylmethyl chloroformate (FMOC-Cl) was done prior to their concentration and purification by solid phase extraction. They were then analyzed by ultra performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). The method was tested in different aqueous matrices with spiking tests and validated for the matrix effect correction in relevant environmental samples. Calibration curves established between 10 and 1000ng/l showed r2 values above 0.989, mean recoveries varied between 86 and 133% and limits of detection and quantification of the method were as low as 5 and 10ng/l respectively. At the parcel scale, two parcels of the Lavaux vineyard area, located near the Lutrive River at 6km to the east of Lausanne, were monitored to assess to which extent glyphosate and AMPA were retained in the soil or exported to surface waters. They were equipped at their bottom with porous ceramic cups and runoff collectors, which allowed retrieving water samples for the growing seasons 2010 and 2011. Results revealed that the mobility of glyphosate and AMPA in the unsaturated zone was likely driven by the precipitation regime and the soil characteristics, such as slope, porosity structure and layer permeability discrepancy. Elevated glyphosate and AMPA concentrations were measured at 60 and 80 cm depth at parcel bottoms, suggesting their infiltration in the upper parts of the parcels and the presence of preferential flow in the studied parcels. Indeed, the succession of rainy days induced the gradual saturation of the soil porosity, leading to rapid infiltration through macropores, as well as surface runoff formation. Furthermore, the presence of more impervious weathered marls at 100 cm depth induced throughflows, the importance of which for the lateral transport of the herbicide molecules was determined by the slope steepness. Important rainfall events (>10 mm/day) were clearly exporting molecules from the soil top layer, as indicated by important concentrations in runoff samples. A mass balance showed that total loss (10-20%) mainly occurred through surface runoff (96%) and, to a minor extent, by throughflows in soils (4%), with subsequent exfiltration to surface waters. Observations made in the Lutrive River revealed interesting details of glyphosate and AMPA dynamics in urbanized landscapes, such as the Lavaux vineyards. Indeed, besides their physical and chemical properties, herbicide dynamics at the catchment level strongly depend on application rates, precipitation regime, land use and also on the presence of drains or constructed channels. Elevated concentrations, up to 4970 ng/l, observed just after the application, confirmed the diffuse export of these compounds from the vineyard area by surface runoff during main rain events. From April to September 2011, a total load of 7.1 kg was calculated, with 85% coming from vineyards and minor urban sources and 15% from arable crops. Small vineyard surfaces could generate high concentrations of herbicides and contribute considerably to the total load calculated at the outlet, due to their steep slopes (~10%). The extrapolated total amount transferred yearly from the Lavaux vineyards to the Lake of Geneva was of 190kg. At the molecular scale, the possible involvement of dissolved organic matter (DOM) in glyphosate and copper transport was studied using UV/Vis fluorescence spectroscopy. Combined with parallel factor (PARAFAC) analysis, this technique allowed characterizing DOM of soil and surface water samples from the studied vineyard area. Glyphosate concentrations were linked to the fulvic-like spectroscopic signature of DOM in soil water samples, as well as to copper, suggesting the formation of ternary complexes. In surface water samples, its concentrations were also correlated to copper ones, but not in a significant way to the fulvic-like signature. Quenching experiments with standards confirmed field tendencies in the laboratory, with a stronger decrease in fluorescence intensity for fulvic-like fluorophore than for more aromatic ones. Lastly, based on maximum concentrations measured in the river, an environmental risk for these compounds was assessed, using laboratory tests and ecotoxicity data from the literature. In our case and with the methodology applied, the risk towards aquatic species was found negligible (RF<1).

Growth, production and quality of pineapple in response to herbicide use

In pineapple fields, weed competition is exacerbated by the fact that the crop is small and has a very slow vegetative development. The objective of this study was to determine the effects of herbicides on growth, yield and quality of pineapple, cultivar 'Pérola'. The experimental design was in randomized blocks with four treatments and four replications. Treatments consisted of weeding by hoe and the herbicides diuron; fluazifop-p-butyl and atrazine + S-metolachlor applied in post-emergence. The characteristics evaluated monthly during the vegetative stage were stem diameter, D-leaf length, number of leaves, number of emitted leaves and percentage of natural floral induction. In the reproductive phase, evaluations were made of average fruit weight (g) with and without crown, fruits length and diameter, number of slip, slip-sucker and sucker type seedlings, determination of soluble solids and pH in the pulp. There was no effect of herbicide treatment on the vegetative growth characteristics. Stem diameter increased until 330 days after planting, showing a decrease after this period. The D-leaf grew over time in all treatments, although phytotoxicity symptoms were observed after the first application of herbicides. The traits evaluated on the reproductive phase showed no significant differences in response to treatments. Therefore, the use of diuron fluazifop-p-butyl and atrazine + S-metolachlor did not affect growth, yield and fruit quality of pineapple, cultivar 'Pérola'.

Atrazine bound residues formation and dissipation in subtropical soil under swine wastewater application

The effects of swine wastewater on atrazine dissipation and formation of bound residues in subtropical clay soil were investigated in this study. The experiment was carried out in laboratory, under room conditions, where samples of Rhodic Hapludox soil received 168.61 mg kg-1 of atrazine and were incubated for 60 days in the following treatments: T1 (sterilized soil + swine wastewater), T2 (sterilized soil + distilled water), T3 (Non sterilized soil + swine wastewater) and T4 (Non sterilized soil + distilled water). The extractable residues and bound residues of atrazine were extracted and analyzed by high performance liquid chromatography. The results showed no effect of swine wastewater on atrazine dissipation. However, the addition of swine wastewater favored the increase of bound residues, which can increase the persistence of atrazine in the environment and reduce its bioavailability.

Effect of dose and application site on quinclorac absorption by barnyardgrass biotypes

This work aimed to evaluate the uptake and translocation of quinclorac in function of application sites (shoot or roots) by Echinochloa crusgalli biotypes resistant and susceptible to this herbicide. The treatments consisted of quinclorac doses (0; 0.5; 1; 2; 4; 16 and 64 ppm), applied on the shoot or roots of seedlings of barnyardgrass biotypes. The experimental units consisted of plastic cups containing 250 cm³ of sand. The treatments were applied 10 days after emergence, when barnyardgrass plants reached a 2- to 3- leaf growth stage. The barnyardgrass biotypes were irrigated with nutritive solution weekly and maintained for 40 days after emergence, when length, fresh and dry matter of shoot and roots were evaluated. Variance analysis was carried out using the F test at 5% probability, and in case of significance, a non-linear regression analysis was also carried out using a three-parameter logistic model. In the susceptible biotype, quinclorac was more absorbed by the roots than by the shoot. Comparing dry mass production of the different plant parts of the susceptible biotype per application site, it was verified that quinclorac action is higher when applied to the plant roots. However, for the resistant biotype, it was not possible to determine the dose causing 50% reduction in dry mass accumulation (GR50) and in the resistance index (RI) between both biotypes, due to its high resistance to quinclorac (128 times the recommended dosage). The results showed that quinclorac resistance by the evaluated biotype is not due to differences in the absorption site, strongly suggesting that the resistance acquired by the biotype may result from alteration in the target site.

Selectivity of glyphosate in tank mixtures for RR soybean in sequential applications with mixtures only in the first or second application

Tank mixtures among herbicides of different action mechanisms might increase weed control spectrum and may be an important strategy for preventing the development of resistance in RR soybean. However, little is known about the effects of these herbicide combinations on soybean plants. Hence, two experiments were carried out aiming at evaluating the selectivity of glyphosate mixtures with other active ingredients applied in postemergence to RR soybean. The first application was carried out at V1 to V2 soybean stage and the second at V3 to V4 (15 days after the first one). For experiment I, treatments (rates in g ha-1) evaluated were composed by two sequential applications: the first one with glyphosate (720) in tank mixtures with cloransulam (30.24), fomesafen (125), lactofen (72), chlorimuron (12.5), flumiclorac (30), bentazon (480) and imazethapyr (80); the second application consisted of isolated glyphosate (480). In experiment II, treatments also consisted of two sequential applications, but tank mixtures as described above were applied as the second application. The first one in this experiment consisted of isolated glyphosate (720). For both experiments, sequential applications of glyphosate alone at 720/480, 960/480, 1200/480 and 960/720 (Expt. I) or 720/480, 720/720, 720/960 and 720/1200 (Expt. II) were used as control treatments. Applications of glyphosate tank mixtures with other herbicides are more selective to RR soybean when applied at younger stages whereas applications at later stages might cause yield losses, especially when glyphosate is mixed with lactofen and bentazon.

Effects of early compost application on no-till organic soybean

Weed control has always been an important issue in agriculture. With the advent of no-till systems, soil erosion was reduced but herbicide use was increased. Organic no-till systems try to adjust reduced erosion to the no use of herbicides. Nevertheless, this adjustment is limited by the cost of mechanical weed control. This cost may be reduced by improved cultural weed control with cover crops mulches. In this paper we report a study on the application of compost manure on an oats winter cover crop, preceding soybean, instead of on the soybean summer crop. Treatments comprised a control without compost manure, and compost manure doses of 4 and 8 Mg ha-1 applied either on oats in winter or soybean in summer, organized in a randomized block design, with five replications. In summer, plots were split into weed-controlled or not controlled subplots. The timing of application and the manure doses did not affect the oats biomass or the soybean performance. However, in summer, without water stress, the application of manure at 8 Mg ha-1 directly on soybean has reduced weed biomass in this crop.

Glyphosate translocation in herbicide tolerant plants

The objective of this study was to evaluate glyphosate translocation in glyphosate-tolerant weed species (I. nil, T. procumbens and S. latifolia) compared to glyphosate-susceptible species (B. pilosa). The evaluations of 14C-glyphosate absorption and translocation were performed at 6, 12, 36 and 72 hours after treatment (HAT) in I. nil and B. pilosa, and only at 72 HAT in the species T. procumbens and S. latifolia. The plants were collected and fractionated into application leaf, other leaves, stems, and roots. In S. latifolia, approximately 88% of the glyphosate remained in the application leaf and a small amount was translocated to roots at 72 HAT. However, 75% of the herbicide applied on T. procumbens remained in the leaf that had received the treatment, with greater glyphosate translocation to the floral bud. It was concluded that the smaller amount of glyphosate observed in S. latifolia and T. procumbens may partly account for their higher tolerance to glyphosate. However, I. nil tolerance to glyphosate may be associated with other factors such as metabolization, root exudation or compartmentalization, because a large amount of the herbicide reached the roots of this species.

Effects of irrigated rice sowing season and imazapyr + imazapic time of application on rice grain yield and red rice management

Irrigated rice sowing season and red rice competition are among the main factors affecting grain yield. The objective of this work was to evaluate the sowing date of irrigated rice and moments of application of the herbicide imazapyr + imazapic to control red rice management and irrigated rice grain yield. Eight experiments were performed at the following dates (09/30, 10/19, 11/08 and 12/01) for the 2010/2011 harvest season and (09/27, 10/17, 11/08 and 12/05) for the 2011/2012 harvest season. The treatments were: application of the herbicide imazapyr + imazapic at doses of 105+35 g ha-1 in pre-emergence (PRE); 52.5+17.5 g ha‑1 in pre-emergence and 52.5+17.5 g ha-1 in post-emergence (PRE + POST); and 105+35 g ha-1 in post- emergence (POST), and a control without application and no weeding. The cultivar Puitá Inta CL was used and a randomized block design with four replicates. A joint analysis of the experiments was carried out. There was less emergence of red rice and higher grain yield of the irrigated rice at the early periods (09/30/10 and 09/27/11), with 10,578 and 8,653 kg ha-1, respectively. At the end of the season (12/01/10 and 12/05/11), there was greater reduction of the red rice seed bank. Sowing at the beginning of the recommended period provided more irrigated rice grain yield. The application of imazapyr + imazapic at a dose of 52.5+17.5 g ha-1 in PRE + 52.5+17.5 g ha-1 POST, and 105+35 g ha-1 only in PRE and POST was effective in the control of red rice.

Resistance of Raphanus raphanistrum to the herbicide metsulfuron-methyl

The ALS-inhibiting herbicides, especially metsulfuron-methyl, are widely used for weed control, mainly wheat and barley in southern Brazil. Raphanus raphanistrum is a major weed of winter crops. However, in recent years, R.raphanistrum, after being treated with metsulfuron, has shown no symptoms of toxicity, possibly due to herbicide resistance. Aiming to evaluate the existence of R.raphanistrum biotypes resistant to metsulfuron, an experiment was conducted in a greenhouse, in a completely randomized design with four replications. The plots consisted of pots with six plants. The treatments consisted of the interaction of resistant R. raphanistrum (biotype R) and susceptible R. raphanistrum (biotypes S) with ten doses of the herbicide (0.0; 0.6; 1.2; 2.4; 4.8; 9.6; 19.2; 38.4; 76.8 and 153.6 g i.a. ha-1). The application of the test herbicides occurred when the crop was at the stage of 3 to 4 true leaves. The variables analyzed were control and dry matter accumulation. Statistical analysis of dose-response curves was performed by non linear regression. Biotype S was susceptible to the herbicide even at doses below the recommended. Biotype R was insensitive to the herbicide obtaining values of resistance factor (F) higher than 85. The dose-response curve confirmed the existence of R. raphanistrum biotypes with high level of resistance to metsulfuron-methyl.

Influence of spray mixture volume and flight height on herbicide deposition in aerial applications on pastures

The objective of the present study was to analyze the influence of spray mixture volume and flight height on herbicide deposition in aerial applications on pastures. The experimental plots were arranged in a pasture area in the district of Porto Esperidião (Mato Grosso, Brazil). In all of the treatments, the applications contained the herbicides aminopyralid and fluroxypyr (Dominum) at the dose of 2.5 L c.p. ha-1, including the adjuvant mineral oil (Joint Oil) at the dose of 1.0 L and a tracer to determine the deposition by high-performance liquid chromatography (HPLC) (rhodamine at a concentration of 0.6%). The experiment consisted of nine treatments that comprised the combinations of three spray volumes (20, 30 and 50 L ha-1) and three flight heights (10, 30 and 40 m). The results showed that, on average, there was a tendency for larger deposits for the smallest flight heights, with a significant difference between the heights of 10 and 40 m. There was no significant difference among the deposits obtained with the different spray mixture volumes.

Imazapyr herbicide efficacy on floating macrophyte control and ecotoxicology for non-target organisms

the aims of this study were to determine imazapyr efficacy for floating macrophyte control and ecotoxicology for non-target organisms. For the floating macrophyte control efficacy tests were used the doses of 0,5; 1,0; 2,0; 2,5; 3,0; 3,5 and 4,0 L ha-1 and a control with 10 replicates. The acute toxicology for non-target organisms was estimated by lethal concentration 50% (LC50 and EC50). The floating macrophyte control efficacy was over 90%. Imazapyr was classified as moderately toxic for the following biomarkers: L. minor, H. eques, B. rerio, P. caudimaculatus, P. canaliculata, and P. mesopotamicus and lightly toxic for A. caroliniana. Thus, imazapyr herbicide is a tool with great potential to be used on floating macrophyte control (E. crassipes, P. stratiotes e S. molesta) in Brazil and this practice can be evaluated by the use of application biomarkers.

Mycorrhizal Association and Microbial Activity of Soil Cultivated with Cassava After Application of Mesotrione and Fluazifop-p-Butyl

Soil is a very heterogeneous environment that allows the establishment of wide range of microorganisms populations, whose balance is affected by biotic and abiotic factors. This study has aimed to assess the effect of doses of mesotrione and fluazifop-p-butyl herbicides and two assessment periods on microbial activity and biomass of soil cultivated with cassava Cacau-UFV cultivar, besides the root colonization by arbuscular mycorrhizal fungi. Two trials were conducted in a protected environment where was realized post-emergence application of mesotrione in the doses of 72, 108, 144 and 216 g ha-1 and fluazifop-p-butyl in the doses of 100, 150, 200 and 300 g ha-1, besides a control without application. Soil samples were collected for determination of soil respiratory rate (RR), microbial biomass carbon (MBC), metabolic quotient (qCO2), and colonization of roots by arbuscular mycorrhizal fungi at the 30 and 60 days after applications (DAA) of the herbicides. Fluazifop-p-butyl increased the RR, MBC and the percentage of cassava roots colonized by mycorrhizal fungi in the assessment performed at 60 DAA. The larger effects of mesotrione on soil microbial indicators were up to 30 DAA, being the changes minimized at 60 DAA. It is concluded that the herbicides alter the soil microbial indicators, with effects dependent of the product, of dose applied and also of the period of assessment.

Application of Sulfentrazone in Stages of Germination of IAC 90 Cassava Cuttings in Clay Soils and Sandy

Weeds interfere dramatically in the productive potential of cassava; however, information regarding herbicides that are selective to crops is still scarce. Thus, the aim in this study was to assess the initial growth of IAC 90 cassava plants after the application of sulfentrazone at different stages of germination of cassava in clayey and sandy soils. Three experiments were simultaneously deployed: the first experiment consisted in the application of sulfentrazone in the non-germinated stage of cassava cuttings; the second one in the stage of germinated cassavas cuttings (0.9 cm shoots); and the third one in applications in the stage of cassava cuttings with buds emerging (6.5 cm shoots and emerging from the soil). For each experiment the experimental design in randomized blocks was used in the 2 x 5 factorial arrangement with four replications. The factors were composed of two soils (sandy and clayey) and five doses of sulfentrazone (0, 250, 500, 750 and 1,000 g ha-1). It was found that depending on the herbicide dose, development stage of the buds of cassava cuttings and the type of soil, damage can occur in the initial development of the IAC 90 cassava plants. The greatest potential of sulfentrazone selectivity has occurred in applications in the non-germinated cassava cuttings stage and in doses lower than 500 g ha-1 in the clayey soil.

EFFECT OF POST-EMERGENCE HERBICIDE APPLICATIONS ON RICE CROP WEED COMMUNITIES IN TOLIMA, COLOMBIA

ABSTRACTThe weed communities of agricultural systems are dynamic and respond to changes in agronomic practices. This study aimed to evaluate the effect of post-emergence herbicide control programs made by farmers on weed communities and commercial lots of rice. The evaluations were carried out in 96 commercial lots located in the Centro, Meseta and Norte zones of the department of Tolima. In each lot, 1 ha was marked off, in which the evaluations were carried out by randomly throwing a 0.2 x 0.2 m sampling-square 5 times. Samples were taken before the first post-emergence application, after the first post-emergence application, after the second post-emergence application, and once the post-emergence applications were finished. The evaluated variables included density and cover of the weeds and the crops. The IVI of each species was calculated and the control program was analyzed in terms of decreases in the number of individuals for the 15 more encountered species. Before the applications, higher density values were found. The first and second post-emergence applications reduced the average density by 41% and 12%, respectively, throughout the department. Between the first and fourth evaluations, the density of the weeds and crops decreased throughout the department by 51.7% and 39%, respectively. The weed density variable proved to be the most influential in the populations after the herbicide programs were carried out.

Changes in Photosynthesis and Oxidative Stress in Wheat Plants Submmited to Herbicides Application

The use of herbicides, even in tolerant crops, can cause stress evidenced by increase phytotoxicity affecting growth and development. The objectives of this study were to evaluate herbicides effect from different mechanisms of action in photosynthetic and oxidative stress parameters, as well visual phytotoxicity and wild radish control in wheat crop, cultivar Quartzo. Two trials were conducted where the first one evaluated the photosynthetic parameters on wheat plants in two seasons collection, following the application of herbicides bentazon, clodinafop, iodosulfuron, metribuzin, metsulfuron and 2,4-D; and the second one evaluated wild radish (Raphanus sativus) control, wheat phytotoxicity and yield due to bentazon, iodosulfuron, metribuzin, metsulfuron and 2,4-D herbicides application. Photosynthetic rate, stomatal conductance and transpiration were negatively affected by metribuzin, metsulfuron and 2,4-D herbicides at 24 and 120 HAS (hours after spraying) compared to control. Oxidative stress was similar or lower to control, when herbicide was applied and, in general, there was no difference between application times. Lipid peroxidation, catalase activity and phenols were higher in the first collection time. The application of herbicides iodosulfuron and 2,4-D reduces chlorophylls and carotenoids in wheat. Herbicides bentazon, iodosulfuron, metribuzin, metsulfuron and 2,4-D are selective to wheat, cultivar Quartzo and do not affect wheat yield. 2,4-D, metribuzin and iodosulfuron are more efficient for wild radish control.