Fate and availability of glyphosate and AMPA in agricultural soil

The fate of glyphosate and its degradation product aminomethylphosphonic acid (AMPA) was studied in soil. Labeled glyphosate was used to be able to distinguish the measured quantities of glyphosate and AMPA from the background values since the soil was sampled in a field where glyphosate had been used formerly. After addition of labeled glyphosate, the disappearance of glyphosate and the formation and disappearance of AMPA were monitored. The resulting curves were fitted according to a new EU guideline. The best fit of the glyphosate degradation data was obtained using a first-order multi compartment (FOMC) model. DT₅₀ values of 9 days (glyphosate) and 32 days (AMPA) indicated relatively rapid degradation. After an aging period of 6 months, the leaching risk of each residue was determined by treating the soil with pure water or a phosphate solution (pH 6), to simulate rain over a non-fertilized or fertilized field, respectively. Significantly larger (p < 0.05) amounts of aged glyphosate and AMPA were extracted from the soil when phosphate solution was used as an extraction agent, compared with pure water. This indicates that the risk of leaching of aged glyphosate and AMPA residues from soil is greater in fertilized soil. The blank soil, to which 252 g glyphosate/ha was applied 21 months before this study, contained 0.81 ng glyphosate/g dry soil and 10.46 ng AMPA/g dry soil at the start of the study. Blank soil samples were used as controls without glyphosate addition. After incubation of the blank soil samples for 6 months, a significantly larger amount of AMPA was extracted from the soil treated with phosphate solution than from that treated with pure water. To determine the degree of uptake of aged glyphosate residues by crops growing in the soil, ¹⁴C-labeled glyphosate was applied to soil 6.5 months prior to sowing rape and barley seeds. After 41 days, 0.006 ± 0.002% and 0.005 ± 0.001% of the applied radioactivity was measured in rape and barley, respectively.     

Microbial transformation products of benzoxazolinone and benzoxazinone allelochemicals--a review

Cyclic hydroxamic acids and lactams are allelochemicals present in the common agricultural crops wheat, rye, and maize. The hydroxamic acids are mainly present in the plants as glucosides. Upon injury or insect attack or when exuded to the soil environment, the hydroxamic acids occur in their unstable agluconic form. In the first step in the transformation of hydroxamic acids, benzoxazolinones are formed spontaneously. It is necessary to elucidate the further microbial transformation of these compounds in the soil environment for a purposeful exploitation of the allelopathic properties of wheat, rye, and maize. In the present paper, the existing knowledge on microbial transformation products of benzoxazolin-2-one (BOA), 6-methoxy-benzoxazolin-2-one (MBOA), and 2-hydroxy-1,4-benzoxazin-3-one (HBOA) was reviewed. Three main groups of transformation products were identified: aminophenoxazinones, malonamic acids, and acetamides. Future research needs concerning the transformation of these chemicals in soil are discussed, when their properties for suppressing weeds and soil-borne diseases are going to be exploited.     

Leaching of pesticides through normal-tillage and low-tillage soil--a lysimeter study. I. Isoproturon

Isoproturon is a herbicide, which was used in Denmark against grass weeds and broad-leaved weeds until 1998. Isoproturon has frequently been detected in ground water monitoring studies. Leaching of isoproturon (N,N-dimethyl-N'-(4-(1-methylethyl)-phenyl)urea) and its metabolites, N'-(4-isopropylphenyl)-N-methylurea and N'-(4-isopropylphenyl)urea was studied in four lysimetres, two of them being replicates from a low-tillage field (lysimeter 3 and 4), the other two being replicates from a normal tillage field (lysimeter 5 and 6). In both cases the soil was a sandy loam soil with 13-14% clay. The lysimetres had a surface area of 0.5 m2 and a depth of 110 cm. Lysimeter 3 and 4 were sprayed with unlabelled isoproturon while lysimeter 5 and 6 was sprayed with a mixture of 14C-labelled and unlabelled isoproturon. The total amount of isoproturon sprayed onto each lysimeter was 63 mg, corresponding to 1.25 kg active ingredient per ha. The lysimeters were sprayed with isoproturon on October 26, 1997. The lysimetres were installed in an outdoor system in Research Centre Flakkebjerg and were thus exposed to normal climatic conditions of the area. A mean of 360 l drainage water were collected from lysimeter 3 and 4 and a mean of 375 litres from lysimeter 5 and 6. Only negligible amounts of isoproturon and its primary metabolites were found in the drainage water samples, and thus no significant difference between the two lysimeter sets was shown. In a total of 82 drainage water samples, evenly distributed between the four lysimetres isoproturon was found in detectable amounts in two samples and N'-(4-isopropylphenyl)urea was found in detectable amounts in two other samples. The detection limit for all the compounds was 0.02 microg/l. 48% and 54% of the added radioactivity were recovered from the upper 10 cm soil layer in lysimeter 5 and 6, respectively, and 17 and 14% from 10-20 cm's depth. By extraction first with an aquatic CaCl2 solution 0.49% of the added radioactivity was extracted from the upper 10 cm layer in lysimeter 5. In the subsequent extraction with acetonitril, 1.19% of the added radioactivity was extracted. In lysimeter 6, upper 10 cm, 0.2% were extracted with water and 0.56% were extracted with acetonitril. Below 10 cm's depth no measurable amounts could be extracted.     

Sorption and degradation of neonicotinoid insecticides in tropical soils

ABSTRACT

Neonicotinoids are the most widely applied class of insecticides in cocoa farming in Ghana. Despite the intensive application of these insecticides, knowledge of their fate in the Ghanaian and sub-Saharan African environment remains low. This study examined the behavior of neonicotinoids in soils from cocoa plantations in Ghana by estimating their sorption and degradation using established kinetic models and isotherms. Studies of sorption were conducted using the batch equilibrium method on imidacloprid, thiamethoxam, clothianidin, acetamiprid and thiacloprid, while degradation of imidacloprid, thiamethoxam and their respective deuterated counterparts was studied using models proposed by the European forum for coordination of pesticide fate and their use (FOCUS). Analytes were extracted using the quick, easy, cheap, effective, rugged and safe (QuEChERS) procedure and quantified by liquid chromatography-tandem mass spectrometry (LC–MS/MS). Average recoveries were high (≥ 85%) for all analytes. The findings from the study suggest that neonicotinoid insecticides may be persistent in the soils studied based on estimated half-lives > 150 days. The study also revealed generally low-sorption coefficients for neonicotinoids in soils, largely influenced by soil organic carbon.     

Degradation of biochanin A in soil

Degradation of biochanin A, 400 μg (1.41 μmol) per gram of dry soil, was studied and the initial degradation products, dihydrobiochanin A, pratensein and genistein were identified and quantified. The maximum concentrations of these compounds were determined as 166 pmol/g dry soil after 2 days of incubation, 175 pmol/g dry soil after 1 day and 1,236 pmol/g dry soil after 1 day, respectively. Biochanin A and the initially formed products degrade too fast to be responsible for clover soil sickness (DT₉₀ <20 days), but could be precursors for the responsible compounds. The immediate degradation products from biochanin A are all biologically active and are the prime candidates for a reduction of weed pressure caused by clover.     

Biologically active secondary metabolites in white clover (Trifolium repens L.) – a review focusing on contents in the plant, plant–pest interactions and transformation

Summary.  To exploit biologically active compounds from white clover (Trifolium repens L.) for suppressing weeds and soil-borne diseases, either as isolated products (biopesticides) or through cultivars with enhanced production of these compounds, the biologically active compounds must be identified, plant content measured, and their fate in soil known. The present review summarizes the published knowledge needed for such exploitation; providing essential information on structure and concentration of flavonols, flavones, condensed tannins, isoflavones, isoflavanones, pterocarpans, coumestans, cyanogenic glucosides, and saponins in healthy and stressed white clover plants. Various stresses and particular cultivars affect the concentrations of several of the compounds. Information on biological effects and the degradation/transformation of these compounds in plants or by microorganisms is available. There is no information on the degradation pathway in soil, the mechanisms of exudation and leaching of compounds from plants, and soil sorption properties of the compounds. The clover soil fatigue problem is increasing in grasslands and causes problems especially in organic farming. Research efforts focused on biological elements of clover soil fatigue have not explained it, and the influence of secondary metabolites has not been investigated. There are few investigations into the interaction between beneficial fungi/fungal-diseases and the occurrence of biologically active secondary metabolites in white clover plants. Such studies are critical to better understand beneficial fungi and pathogens.     

Fate and availability of glyphosate and AMPA in agricultural soil

The fate of glyphosate and its degradation product aminomethylphosphonic acid (AMPA) was studied in soil. Labeled glyphosate was used to be able to distinguish the measured quantities of glyphosate and AMPA from the background values since the soil was sampled in a field where glyphosate had been used formerly. After addition of labeled glyphosate, the disappearance of glyphosate and the formation and disappearance of AMPA were monitored. The resulting curves were fitted according to a new EU guideline. The best fit of the glyphosate degradation data was obtained using a first-order multi compartment (FOMC) model. DT(50) values of 9 days (glyphosate) and 32 days (AMPA) indicated relatively rapid degradation. After an aging period of 6 months, the leaching risk of each residue was determined by treating the soil with pure water or a phosphate solution (pH 6), to simulate rain over a non-fertilized or fertilized field, respectively. Significantly larger (p < 0.05) amounts of aged glyphosate and AMPA were extracted from the soil when phosphate solution was used as an extraction agent, compared with pure water. This indicates that the risk of leaching of aged glyphosate and AMPA residues from soil is greater in fertilized soil. The blank soil, to which 252 g glyphosate/ha was applied 21 months before this study, contained 0.81 ng glyphosate/g dry soil and 10.46 ng AMPA/g dry soil at the start of the study. Blank soil samples were used as controls without glyphosate addition. After incubation of the blank soil samples for 6 months, a significantly larger amount of AMPA was extracted from the soil treated with phosphate solution than from that treated with pure water. To determine the degree of uptake of aged glyphosate residues by crops growing in the soil, (14)C-labeled glyphosate was applied to soil 6.5 months prior to sowing rape and barley seeds. After 41 days, 0.006 +/- 0.002% and 0.005 +/- 0.001% of the applied radioactivity was measured in rape and barley, respectively.     

Transformation kinetics of 6-methoxybenzoxazolin-2-one in soil

Wheat (Triticum aestivum L.) and other cereals produce allelochemicals as natural defense compounds against weeds, fungi, insects and soil-borne diseases. The main benzoxazinoid allelochemical of wheat is 2,4-dihydroxy-7-methoxy-1,4-benzoxazin-3-one (DIMBOA), bound as beta-glucoside and released upon plant injury. When leached from wheat to soil, DIMBOA is microbially transformed to 6-methoxy-benzoxazolin-2-one (MBOA). Exploiting benzoxazinoids and their degradation products as substitutes for synthetic pesticides depends on knowledge of transformation pathways and kinetics. In an MBOA degradation experiment at a concentration of 2400 nmol g(-1) soil, the previously identified transformation products 2-amino-7-methoxy-phenoxazin-3-one (AMPO) and 2-acetylamino-7-methoxy-phenoxazin-3-one (AAMPO) were quantified. Three different kinetic models were applied to MBOA transformation kinetics; single first-order (SFO), first-order multi-compartment, and double first-order in parallel. SFO proved to be adequate and was subsequently applied to the transformations of MBOA, AMPO and AAMPO. Degradation endpoints, expressed as degradation time (DT), were calculated for MBOA, AMPO and AAMPO to test whether the maximum values for synthetic pesticides set by the European Commission and the Danish Environmental Protection Agency were exceeded. DT(50) values for MBOA and AMPO were 5.4 d and 321.5 d, respectively, and DT(90) values were 18.1 d and 1068 d, respectively. The DT(50) value for AMPO exceeded the maximum value. The persistence, concentrations and toxicity of metabolites such as AMPO should be considered when breeding cereal crops with increased levels of benzoxazinoids.     

Transformation products of 2-benzoxazolinone (BOA) in soil

Three degradation experiments were performed to examine the formation of transformation products from 2-benzoxazolinone (BOA) in different soil types and concentrations. In two experiments using BOA in low concentration (400 microgkg(-1)) only one unidentified transformation product was found, whereas in the degradation experiment in high concentration (400 mgkg(-1)) several metabolites occurred. Two of these metabolites, 2-amino-(3H)-phenoxazin-3-one (APO); and 2-acetylamino-(3H)-phenoxazin-3-one (AAPO) were synthesized to prove their identity. This is the first time that the successive formation of these types of compounds from BOA is shown in soil. A number of other APO related transformation products were detected and provisionally characterized. The formation of APO, which is a much more biologically active compound than BOA, and the concurrent formation of a number of other APO-related metabolites in soil underline the importance of performing transformation studies as part of the evaluation of the effect of allelochemicals on weeds and soil-borne diseases.     

Leaching of pesticides through normal-tillage and low-tillage soil--a lysimeter study. II. Glyphosate

Glyphosate is a widely used non-selective herbicide. Leaching of glyphosate (N-(phosphonomethyl)glycine) and/or its metabolite AMPA (aminomethylphosphonic acid) was studied in four lysimeters, two of them being replicates from a low-tillage field (lysimeter 3 and 4), the other two being replicates from a normal tillage field (lysimeter 5 and 6). In both cases the soil was a sandy loam soil with 13-14% clay. The lysimeters had a surface area of 0.5 m2 and a depth of 110 cm. Lysimeter 3 and 4 were sprayed with a mixture of 14C-labelled glyphosate and unlabelled glyphosate, while lysimeter 5 and 6 were sprayed with unlabelled glyphosate. The spraying took place September 18, 1997. The total amount of glyphosate sprayed onto each lysimeter was 40 mg, corresponding to 0.8 kg active ingredient per ha. The lysimeters were installed in an outdoor system in Research Centre Flakkebjerg and were thus exposed to normal climatic conditions of the area. A mean of 260 l drainage water were collected from lysimeter 3 and 4 and a mean of 375 litres from lysimeter 5 and 6. The mean yearly concentration of leached glyphosate and/or AMPA was significantly below 0.1 microg/l from both sets of lysimeters, and thus no significant difference between the two lysimeter sets was shown. However, in both sets of lysimeters several single findings at concentrations above 0.1 microg/l was seen, which might be due to the leaching of particle-bound compounds. A significant difference between the soil residual concencentrations of AMPA was seen, the higher concentration was found in the set of lysimeter where low-tillage had been practiced and where Round Up had been used several times in the years before sampling of the lysimeter soil.