Soil bound residues of carbaryl and 1‐naphthol: Release and mineralization in soil,and uptake by plants

Abstract

¹⁴C‐carbaryl and ¹⁴C‐1‐naphthol form soil bound residues which get partially released when barley was grown. ¹⁴C‐residues could be detected in both shoot and root in the case of carbaryl treatment while only roots showed ¹⁴C‐residues in the case of 1‐naphthol. Flooding enhanced release of the bound residues while soil amendment did not. There was greater mineralization of bound residues of carbaryl than that of 1‐naphthol. Rice straw amendment enhanced mineralization.     

Laboratory studies on volatilization and mineralization of 14c‐p,p'‐DDT in soil,release of bound residues and dissipation from solid surfaces

Abstract

In support of field data, laboratory studies were conducted on volatilization, mineralization and binding of ¹⁴C‐p,p'‐DDT in soils at Sao Paulo. Incubation of soil for 6 weeks did not result in volatilized organics or mineralization; with >95% extractable radiocarbon in the form of p,p'‐DDT. Small amounts of bound residues (1.8%) were detected in soil. These data confirm the very slow dissipation of DDT in the field which presumably relates to the acidic pH of soil (4.5–4.8).

Bound ¹⁴C‐residues in soils treated with ¹⁴C‐p,p'‐DDT at Praia Grande and Sao Paulo could be released (5–21%) by sulphuric acid treatment. The released residue had the composition: 69–90% DDT, 7–32% DDD and 0–3% DDE. Incubation of soil bound ¹⁴C‐residues with fresh inoculum for 3 months did not result in release of ¹⁴C.

Dissipation from wooden surfaces was fairly slow. After 20 weeks, 74% of the applied radioactivity could be recovered; 44% hexane‐non‐extractable.     

Aged and bound herbicide residues in soil and their bioavailability part 2: Uptake of aged and non‐extractable (bound) [carbonyl‐14C] methabenzthiazuron residues by maize

Abstract

[Carbonyl‐ C]methabenzthiazuron (MBT) was applied to growing winter wheat in an outdoor lysimeter. The amount applied corresponded to 4 kg Tribunil/ha. 140 days after application the 0–2,5 cm soil layer was removed from the lysimeter. This soil contained about 40 % of the applied radioactivity. Using 0,01 M CaCl₂ solution or organic solvents, the extractable residues were removed from the soil. The bioavailability of the non‐extractable as well as aged residues remaining in the soil was investigated in standardized microecosystems containing 1.5 kg of dry soil. During a 4 weeks period the total uptake (4 maize plants/pot) amounted up to 3,6; 2,2; and 0,9 % of the radioactivity from soils containing aged MBT residues, MBT residues non‐extractable‐with 0,01 MCaCl₂ or MBT residues non‐extractable with organic solvents, respectively. About 20 % of the radioactivity found in maize leaves represented chromatographically characterized parent compound. At the end of the plant experiment the soil was extracted again with 0,01 M CaCl₂ and with organic solvents. The soil extracts and also the organic phases obtained from the aqueous fulvic acid solution contained unchanged parent compound.     

Fate in soil of 14C-sulfadiazine residues contained in the manure of young pigs treated with a veterinary antibiotic

The fate of ¹⁴C-labeled sulfadiazine (¹⁴C-SDZ) residues was studied in time-course experiments for 218 days of incubation using two soils (A_p horizon of loamy sand, orthic luvisol; A_p horizon of silt loam, cambisol) amended with fresh and aged (6 months) ¹⁴C-manure [40 g kg^?1 of soil; 6.36 mg of sulfadiazine (SDZ) equivalents per kg of soil], which was derived from two shoats treated with ¹⁴C-SDZ. Mineralization of ¹⁴C-SDZ residues was below 2% after 218 days depending little on soil type. Portions of extractable ¹⁴C (ethanol-water, 9:1, v/v) decreased with time to 4–13% after 218 days of incubation with fresh and aged ¹⁴C-manure and both soils. Non-extractable residues were the main route of the fate of the ¹⁴C-SDZ residues (above 90% of total recovered ¹⁴C after 218 days). These residues were high immediately after amendment depending on soil type and aging of the ¹⁴C-manure, and were stable and not remobilized throughout 218 days of incubation. Bioavailable portions (extraction using CaCl₂ solution) also decreased with increasing incubation period (5–7% after 218 days). Due to thin-layer chromatography (TLC), 500 μg of ¹⁴C-SDZ per kg soil were found in the ethanol-water extracts immediately after amendment with fresh ¹⁴C-manure, and about 50 μg kg^?1 after 218 days. Bioavailable ¹⁴C-SDZ portions present in the CaCl₂ extracts were about 350 μg kg^?1 with amendment. Higher concentrations were initially detected with aged ¹⁴C-manure (ethanol-water extracts: 1,920 μg kg^?1; CaCl₂ extracts: 1,020 μg kg^?1), probably due to release of ¹⁴C-SDZ from bound forms during storage. Consistent results were obtained by extraction of the ¹⁴C-manure-soil samples with ethyl acetate; portions of N-acetylated SDZ were additionally determined. All soluble ¹⁴C-SDZ residues contained in ¹⁴C-manure contributed to the formation of non-extractable residues; a tendency for persistence or accumulation was not observed. SDZ's non-extractable soil residues were associated with the soluble HCl, fulvic acids and humic acids fractions, and the insoluble humin fraction. The majority of the non-extractable residues appeared to be due to stable covalent binding to soil organic matter.     

Chemical and biological release of 14C‐bound residues from soil treated with 14C‐p,p'‐DDT

Abstract

¹⁴C‐p,p'‐DDT‐bound residues in soil can be released by treatment with concentrated sulphuric acid at ambient temperatures. Within 6 days, about 70% of the bound residues was released. Bound residues released after 9 months incubation with ¹⁴C‐DDT showed the presence of DDT and DDE only while bound residues released after 18 months, contained in addition 13% DDD.

Release of bound ¹⁴C‐residues also occurs readily following inoculation of the soil‐bound residues with fresh soil or with individual microorganisms. Almost complete release of bound residues was observed after incubation for 45 days. The rate of release was rapid during the first two weeks and decreased thereafter. TLC and HPLC analysis showed that the released residues contained DDE (about 80%) and a smaller amount of DDD. The disappearance of DDT from the released residues may be attributed to its microbiological degradation to DDE and DDD, shortly after its release.     

Biological activity and bioavailability of grain bound 14C‐malathion residues in rats

Abstract

Paddy (unmilled rice), milled rice and maize‐bound ¹⁴C residues were prepared using ¹⁴C‐succinate‐labelled malathion at 10 and 152 ppm. After 3 months, the bound residues accounted for 12%, 6.5% and 17.7% of the applied dose in paddy, milled rice and maize respectively in the grains treated at 10 ppm. The corresponding values for the 152 ppm were 16.6%, 8.5% and 18.8%. Rats fed milled rice ‐ bound ¹⁴C‐residues eliminated 61% of the ¹⁴C in the faeces and 28% in the urine. The corresponding percentages for paddy and maize were 72%, 9% and 53%, 41% respectively; indicating that bound residues from milled rice and maize were moderately bioavailable. When rice‐bound malathion residues (0.65 ppm in feed) were administered to rats in a 5 week feeding study, no signs of toxicity were observed. Plasma and RBC cholinesterase activities were slightly inhibited: blood urea nitrogen was significantly elevated in the test animals. Other parameters examined showed no or marginal changes.     

Influence of the amendment of corn straw on the degradation behaviour of the fungicide dithianon in soil

Degradation studies were conducted with the fungicide (14)C-dithianon under standard conditions for 64 days in soil. The compound is characterized by mineralization losses of approx. 33% and the formation of non-extractable (bound) residues of approx. 63% in 64 days. The microbial activity of the soil was stimulated by an amendment of corn straw simulating post-harvest conditions. This addition of straw decreased the mineralization of the compound initially. At the end of the incubation period, however, the mineralization rate was higher in the straw amended soil compared to the control. The addition of straw increased the amount of radiocarbon in the desorption solutions. Thus higher amounts of incorporated radiocarbon could be found in the biomass of the amended soil. Model calculations show that the straw amendment has a sustained influence on the mineralization of the compound. Potential mechanisms of the effect of dissolved organic matter on the sorption/desorption equilibrium are discussed.     

Fate of the veterinary antibiotic 14C-difloxacin in soil including simultaneous amendment of pig manure with the focus on non-extractable residues

The fate of ¹⁴C-labeled difloxacin (¹⁴C-DIF) was studied in time course experiments after application on soil (Ap horizon of silt loam) and amendment of authentic DIF containing pig manure (146 mL kg^?1; 4.17 MBq kg^?1; 0.85 mg kg^?1) or water (124 mL kg^?1; 0.42 MBq kg^?1; 0.09 mg kg^?1) for 56 and 120 days of incubation, respectively.

Mineralization of ¹⁴C-DIF was below 0.2% in both experiments after 56 days or 120 days. In the course of the experiments, portions of extractable radioactivity (Accelerated Solvent Extraction (ASE); acetonitrile-water) decreased to 19–21% depending only little on manure amendment. Non-extractable residues of ¹⁴C-DIF increased to 70–74% after 56 days and 120 days, respectively, and therefore were the main route of ¹⁴C-DIF in soil. According to radioanalytical HPLC and LC-MS/MS, only the parent compound was found in all extracts over the whole time of the experiment. According to fractionation of the non-extractable residues (NER) into particle size fractions, ¹⁴C portions were associated to the water used for fractionation, the silt and clay fractions, whereas no radioactivity was detected in the sand fraction. The majority of ¹⁴C was found within the clay fractions.

Fractionation of humic components showed that radioactivity derived from ¹⁴C-DIF was associated with humic acids, fulvic acids, humins and minerals and very little with soluble, non-humic HCl fraction. The highest portions of radioactivity were found in the fulvic acid fraction. Results obtained by size exclusion chromatography (SEC) of the purified fulvic acids were similar for every sample analyzed. One large portion of ¹⁴C co-eluted with fulvic acids of a molecular weight below 910 g mol^?1. Both fractionation methods demonstrated that the parent compound DIF or initial metabolites were rapidly integrated into humic materials and, thus, were major components of NER.     

Plant availability of bound anilazine residues in a degraded loess soil

Abstract

The relative biological availability of [benzene ring‐U‐¹⁴C] and Ctriazine‐U‐¹⁴C] anilazine for maize plants was studied in a degraded loess soil in a standardized microecosystem. The total uptake of radiocarbon in the course of the 4‐week experiment was 3.1 and 4 % respectively of the radioactivity applied if anilazine was uniformly mixed into the soil immediately before beginning the experiment. However, if anilazine was subjected to a degradation at 65 % of the maximum water holding capacity of the soil and temperatures varying daily between 16 and 27°C for 100 days before the plant experiment then the uptake was reduced to 0.4 or 0.7 % respectively. The uptake from soil with non‐extractable (bound) anilazine residues was similarly low. The mineralization rate of aged and bound anilazine residues was below 0.1 % of the radioactivity applied. Up to 2/3 of the radioactivity present in the soil after the plant experiment remained in the humic fraction.     

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.     

Aged and bound herbicide residues in soil and their bioavailability. Part 2: Uptake of aged and non-extractable (bound) [carbonyl-14C]methabenzthiazuron residues by maize

[Carbonyl-14C]methabenzthiazuron (MBT) was applied to growing winter wheat in an outdoor lysimeter. The amount applied corresponded to 4 kg Tribunil/ha. 140 days after application the 0-2.5 cm soil layer was removed from the lysimeter. This soil contained about 40% of the applied radioactivity. Using 0,01 M CaCl2 solution or organic solvents, the extractable residues were removed from the soil. The bioavailability of the non-extractable as well as aged residues remaining in the soil was investigated in standardized microecosystems containing 1.5 kg of dry soil. During a 4 weeks period the total uptake (4 maize plants/pot) amounted up to 3.6; 2.2; and 0.9% of the radioactivity from soils containing aged MBT residues, MBT residues non-extractable with 0.01 M CaCl2 or MBT residues non-extractable with organic solvents, respectively. About 20% of the radioactivity found in maize leaves represented chromatographically characterized parent compound. At the end of the plant experiment the soil was extracted again with 0.01 M CaCl2 and with organic solvents. The soil extracts and also the organic phases obtained from the aqueous fulvic acid solution contained unchanged parent compound.     

Biodegradation of Trifluralin in Harran Soil

Abstract

Degradation of trifluralin (α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine) was investigated in soils taken from three different locations at Harran region of Turkey under laboratory conditions. Surface (0–10 cm) soils, which were taken from a pesticide untreated field Gürgelen, Harran-1 and Ikizce regions in the Harran Plain, were incubated in biometer flasks for 350 days at 25°C. Ring-UL-¹⁴C-trifluralin was applied at the rate of 2 µg g^?1 with 78.7 kBq radioactivity per 100 g soil flask. Evolved ¹⁴CO₂ was monitored in KOH traps throughout the experiment. Periodically, soil sub-samples were removed and extracted by supercritical fluid extraction (SFE). Unextractable soil-bound ¹⁴C residues were determined by combustion. During the 350 days incubation period 6.6, 5.4, and 3.3% of the applied radiocarbon was evolved as ¹⁴CO₂ from the Harran-1, Gürgelen, and Ikizce soil, respectively. At the end of 350 days the SFE-extractable and bound ¹⁴C-trifluralin residues were 39.0 and 29.2% of the initially applied herbicide in Gürgelen soil. The corresponding values for Harran-1 and Ikizce soils were 36.2, 28.4% and 41.6, 18.5% respectively.     

Comparative studies of the fate of atrazine‐14C and pentachlorophenol‐14C in various laboratory and outdoor soil‐plant systems

Abstract

Mass balance and fate of atrazine‐ ¹⁴C and pentachlorophenol‐ ¹⁴C (PCP‐ ¹⁴C) were studied in short‐term tests in a closed aerated laboratory soil‐plant system, using two concentrations in soil and two plant species, as well as under outdoor conditions for one vegetation period. In the laboratory, for both pesticides bioaccu‐mulation factors of radiocarbon taken up by the roots into plants were low. They were higher for lower (1 ppm) than for higher soil concentrations (6 ppm for atra‐zine, 4 ppm for pentachlorophenol) and varied with the plant species. Mineralization to ¹⁴CO₂ in soil was negatively related to soil concentration only for PCP‐ ¹⁴C. Conversion rates in soil including the formation of soil‐bound residues were higher for the lower concentrations of both pesticides than for the higher ones; conversion rates in plants were species‐dependent. In 14 terms of CO₂ formation and of conversion rates, PCP was less persistent in soil than was atrazine. For both pesticides, laboratory data on conversion and mineralization gave a rough prediction of their persistence in soil under long‐term outdoor conditions, whereas bio‐accumulation factors in plants under long‐term outdoor conditions could not be predicted by short‐term laboratory experiments.     

Concentration and dissipation of chlorantraniliprole and thiamethoxam residues in maize straw,maize, and soil

To study the dissipation rates and final residual levels of chlorantraniliprole and thiamethoxam in maize straw, maize, and soil, two independent field trials were conducted during the 2014 cropping season in Beijing and Anhui Provinces of China. A 40% wettable powder (20% chlorantraniliprole?+?20% thiamethoxam) was sprayed onto maize straw and soil at an application rate of 118 g of active ingredient per hectare (g a.i.ha^?1). The residual concentrations were determined by ultra-high-performance liquid chromatography–tandem mass spectrometry. The chlorantraniliprole half-lives in maize straw and soil were 9.0–10.8 and 9.5–21.7 days, respectively. The thiamethoxam half-lives in maize straw and soil were 8.4–9.8 and 4.3–11.7 days, respectively. The final residues of chlorantraniliprole and thiamethoxam in maize straw, maize, and soil were measured after the pesticides had been sprayed two and three times with an interval of 7 days using 1 and 1.5 times the recommended rate (72 g a.i. ha^?1 and 108 g a.i. ha^?1, respectively). Representative maize straw, maize, and soil samples were collected after the last treatment at pre-harvest intervals of 7, 14, and 28 days. The chlorantraniliprole residue was below 0.01 mg kg^?1 in maize, between 0.01 and 0.31 mg kg^?1 in maize straw, and between 0.03 and 1.91 mg kg^?1 in soil. The thiamethoxam residue concentrations in maize, maize straw, and soil were <0.01, <0.01, and 0.01–0.03 mg kg^?1, respectively. The final pesticide residues on maize were lower than the maximum residue limit (MRL) of 0.02 mg kg^?1 after a 14-day pre-harvest interval. Therefore, a dosage of 72 g a.i. ha^?1 was recommended, as it can be considered safe to human beings and animals.     

The acute toxicity of nickel to freshwater ciliates

The degradation of the (14)C-labelled fungicide dithianon in an orthic luvisol was investigated under standardized conditions in comparison to stimulated microbial activity by an amendment of maize straw. The compound is characterized by mineralization losses of approximately 33% and the formation of non-extractable bound residues of approximately 63% in 64 days. Despite the major role of microorganisms in mineralizing this compound, the formation of bound residues is not biotically induced. Gel permeation chromatography and polyacrylamide gel electrophoresis, as different size separation techniques of the humic acids fractions, showed differences in the distribution patterns of non-extractable residues depending on the addition of straw material. The results presented support the existence of humic substances in soil as a micellar system rather than as a biopolymer.     

Fate of 14C‐allylalcohol herbicide in soils and crop residues

Abstract

Residue disappearance and leaching of ¹⁴C‐allyl‐alcohol from different soils were studied in laboratory experiments. Additionally, the uptake of residues by lettuce and carrots was investigated in the greenhouse. In laboratory experiments, residue disappearance and leaching from soils was correlated negatively to the organic matter content. In greenhouse experiments with a sandy loam soil at an application rate normally used in practice, an average of 12.5 % of the applied radioactivity was recovered after an eight day interval between application and sowing. Furthermore, an average of 8 % (sum in soil and plants) of the applied radioactivity was recovered after lettuce or carrot growing. Uptake of residues was higher by carrots than by lettuce, and higher by lettuce roots than by lettuce tops. No bioaccumulation was observed. The residues in soils and plants were, to a high percentage, unextractable and, to a smaller extent, fully water‐soluble products. Unchanged allylalcohol could not be detected by the analytical methods used.     

Ageing processes and soil microbial community effects on the biodegradation of soil C-2,4-D nonextractable residues

The biodegradation of nonextractable residues (NER) of pesticides in soil is still poorly understood. The aim of this study was to evaluate the influence of NER ageing and fresh soil addition on the microbial communities responsible for their mineralisation. Soil containing either 15 or 90-day-old NER of ¹³C-2,4-D (NER15 and NER90, respectively) was incubated for 90 days with or without fresh soil. The addition of fresh soil had no effect on the mineralisation of NER90 or of SOM, but increased the extent and rate of NER15 mineralisation. The analyses of ¹³C-enriched FAME (fatty acids methyl esters) profiles showed that the fresh soil amendment only influenced the amount and structure of microbial populations responsible for the biodegradation of NER15. By coupling biological and chemical analyses, we gained some insight into the nature and the biodegradability of pesticide NER.     

The formation of bound residues of diazinon in four UK soils: implications for risk assessment

The behaviour of diazinon in the soil determines the likelihood of further pollution incidents, particularly leaching to water. The most significant processes in the control of the fate of diazinon in the soil are microbial degradation and the formation of bound residues. Soils from four sites in the UK were amended with diazinon and its ¹⁴C labelled analogue and incubated for 100 days. After 0, 10, 21, 50 and 100 days, the formation of bound residues was assessed by solvent extraction, and the microbial degradation of diazinon by mineralisation assay. In microbially active soils, diazinon is degraded rapidly, reducing the risk of future pollution incidents. However, where there was limited mineralisation there was also significantly lower formation of bound residues, which may lead to water pollution via leaching. The formation of bound residues was dependent on extraction type. Acetonitrile extraction identified bound residues in all soils, with the bound residue fraction increasing with increasing incubation time.     

Impact of repeated pesticide applications on the binding and release of methyl 14C-monocrotophos and U-ring labelled 14C-carbaryl to soil matrices under field conditions

The dissipation of (O-methyl-¹⁴C) monocrotophos and U-ring labelled ¹⁴C-carbaryl was monitored for over two years in absence and presence of other insecticides using in situ soil columns. The dissipation of ¹⁴C-monocrotophos from soil treated with methomyl and carbaryl showed a faster rate of downward movement than in a control column tagged with the labelled insecticide alone. The same trend was observed in experiments with ¹⁴C-carbaryl that dissipated more readily in soil treated with non-labelled monocrotophos and methomyl. In the presence of other insecticides the percentage of bound residues was generally lower than in control experiments. The bound residues at the top of the column are released at a low rate under conditions prevailing in the field. The overall time required for dissipation of 50% of monocrotophos and carbaryl (t₅₀) as estimated from control experiment was approximately 20 and 24 weeks, respectively. The data indicate that repeated applications of pesticides might enhance the release of ¹⁴C-bound residues.     

Release of soil bound (nonextractable) residues by various physiological groups of microorganisms∗

Abstract

Soil bound ¹⁴C‐labeled residues were released by four different physiological groups of microorganisms from an organic soil treated with ¹⁴C‐ring‐labeled prometryn [2‐(methylthio) ‐4,6‐bis(isopropylamino)‐s‐triazine]. The extent to which the different microbial populations released bound ¹⁴C residues (25–30% of the total bound ¹⁴C) from the Y‐irradiated soil after 28 days incubation did not differ considerably. Analysis of the extractable material from the incubated soil showed the presence of small amounts of the parent compound, and its hydroxy and mono‐N‐dealkylated analogues. Low level of ¹⁴CO₂ (1.5–3.0% of the total bound ¹⁴C) was evolved from the microbial systems indicating ring cleavage of the released material as being a very minor reaction.