High-performance liquid chromatography (HPLC) as a tool for monitoring the fate of fluazinam in soil

Fluazinam is a widely used pesticide employed against the fungal disease late blight in potato cultivation. A specific, repeatable, and rapid high-performance liquid chromatography (HPLC) method utilizing a diode array detector (DAD) was developed to determine the presence of fluazinam in soil. The method consists of acetonitrile (ACN) extraction, clean-up with solid-phase extraction (SPE), and separation using a mobile phase consisting of 70% ACN and 30% water (v/v), including 0.02% acetic acid. HPLC was performed with a C18 column and the detection wavelength was 240 nm. The method was successfully applied to an incubation experiment and to soil samples taken from potato fields where fluazinam had been applied two to three times during the on-going growing season. In the 90-day incubation experiment, analytical standard fluazinam and the commercial fungicide Shirlan^® were added to soil samples that had never been treated with fluazinam, and were then extracted with ACN and 0.01 M calcium chloride (CaCl₂). Fluazinam was not extractable with CaCl₂, indicating that it does not leach to watercourses in the dissolved form. Recovery with ACN extraction for sandy soils was 72–95% immediately after application and 53–73% after 90 days of incubation. Out of the eight potato field soil samples, fluazinam was found in two samples at concentrations of 2.1 mg kg^?1 and 1.9 mg kg^?1, well above the limit of quantification (0.1 mg kg^?1).     

The influence of organic matter on sorption and fate of glyphosate in soil - Comparing different soils and humic substances

Soil organic matter (SOM) is generally believed not to influence the sorption of glyphosate in soil. To get a closer look on the dynamics between glyphosate and SOM, we used three approaches: I. Sorption studies with seven purified soil humic fractions showed that these could sorb glyphosate and that the aromatic content, possibly phenolic groups, seems to aid the sorption. II. Sorption studies with six whole soils and with SOM removed showed that several soil parameters including SOM are responsible for the strong sorption of glyphosate in soils. III. After an 80 day fate experiment, ∼40% of the added glyphosate was associated with the humic and fulvic acid fractions in the sandy soils, while this was the case for only ∼10% of the added glyphosate in the clayey soils. Glyphosate sorbed to humic substances in the natural soils seemed to be easier desorbed than glyphosate sorbed to amorphous Fe/Al-oxides.     

Effect of organic amendment on degradation and formation of bound residues of methabenzthiazuron in soil under constant climatic conditions

Abstract

The degradation of [phenyl‐U‐¹⁴C]methabenzthiazuron (MBT) and formation of bound residues in the surface soil of an orthic luvisol were studied under constant climatic conditions (20°C, 40 % of maximum water holding capacity). In two treatments (with and without preincubation in the soil) maize straw was amended at a rate of 1.5 g/100 g dry soil in addition to the application of MBT. The mineralization of uniformly labeled maize straw was studied simultaneously. In additional flasks, MBT was incubated at 0, 10 and 30°C with and without addition of maize straw.

The turnover of the amended maize straw led to an enhanced dissipation of MBT which was mainly due to the formation of bound residues. This corresponded to a higher microbial activity in the soil after straw amendment and the intensive mineralization of the radiolabeled maize straw. About 2–3 % of the applied radioactivity from the radiolabeled maize straw was measured in the soil microbial biomass 10 and 40 days after application whereas ¹⁴C from MBT was only incorporated into soil microbial biomass in the treatments with straw amendment.

Within the bound residue fractions relatively more radioactivity was measured in fulvic and humic acids after straw amendment. Increasing temperatures promoted the dissipation of MBT and the formation of bound residues in both treatments, but without amendment of maize straw these effects were far less pronounced. The laboratory scale degradation experiment led to similar results as were found in a corresponding lysimeter study. Differences that were observed could be explained by different temperature regimes of the experiments and time of aging in soil.     

The effect of multiple soil applications of disulfoton on enhanced microbial degradation in soil and subsequent uptake of insecticidal chemicals by potato plants

Abstract

Potatoes were grown during 1992 in 2 m² plots of loam which had received 1, 2 or 3 annual treatments of Di‐Syston 15G, equivalent to 3.36 kg AI/ha, in furrow at planting. The presence of enhanced degradative activity to the sulfoxide and sulfone metabolites of disulfoton in the soil treated in the previous two years was confirmed by laboratory tests prior to the 1992 treatments. Soil, seed potato and foliage from the three treatments were analyzed for disulfoton and its sulfoxide and sulfone metabolites for 12 wk following planting/treatment. Disulfoton was the major insecticidal component of the soil, a minor component of the seed piece and was not detected (<0.02 ppm) in potato foliage. Disulfoton concentrations in each of the three substrates sampled were similar for the three treatments. Disulfoton sulfoxide and sulfone were the major insecticidal components of the seed piece and foliage. Their maximum concentrations in 1st year soil, seed pieces and foliage were ca. 2x, 2x and 6x, respectively, those measured in the 2nd and 3rd year treatments. The results demonstrate that enhanced microbial degradation of relatively minor insecticidal compounds in the soil can profoundly affect insecticide levels in the plant when these compounds are the major insecticidal components accumulated. The broader implications for crop protection using soil‐applied systemic insecticides are discussed.     

Aflatoxin decomposition in various soils

Abstract

The persistence of aflatoxin in the soil environment could potentially result in a number of adverse environmental consequences. To determine the persistence of aflatoxin in soil, ¹⁴C‐labeled aflatoxin B₁, was added to silt loam, sandy loam, and silty clay loam soils and the subsequent release of ¹⁴CO₂ was determined. After 120 days of incubation, 8.1% of the original aflatoxin added to the silt loam soil was released as CO₂ ? Aflatoxin decomposition in the sandy loam soil proceeded more quickly than the other two soils for the first 20 days of incubation. After this time, the decomposition rate declined and by the end of the study, 4.9% of the aflatoxin was released as CO_2. Aflatoxin decomposition proceeded most slowly in the silty clay loam soil. Only 1.4% of aflatoxin added to the soil was released as CO₂ after 120 days incubation. To determine whether aflatoxin was bound to the silty clay loam soil, aflatoxin B₁ was added to this soil and incubated for 20 days. The soil was periodically extracted and the aflatoxin species present were determined using thin layer chromatographic (TLC) procedures. After one day of incubation, the degradation products, aflatoxins B₂ and G₂, were observed. It was also found that much of the aflatoxin extracted from the soil was not mobile with the TLC solvent system used. This indicated that a conjugate may have formed and thus may be responsible for the lack of aflatoxin decomposition.     

Elevated carbon dioxide does not offset loss of soil carbon from a corn-soybean agroecosystem

The potential for storing additional C in U.S. Corn Belt soils - to offset rising atmospheric [CO₂] - is large. Long-term cultivation has depleted substantial soil organic matter (SOM) stocks that once existed in the region's native ecosystems. In central Illinois, free-air CO₂ enrichment technology was used to investigate the effects of elevated [CO₂] on SOM pools in a conservation tilled corn-soybean rotation. After 5 and 6 y of CO₂ enrichment, we investigated the distribution of C and N among soil fractions with varying ability to protect SOM from rapid decomposition. None of the isolated C or N pools, or bulk-soil C or N, was affected by CO₂ treatment. However, the site has lost soil C and N, largely from unprotected pools, regardless of CO₂ treatment since the experiment began. These findings suggest management practices have affected soil C and N stocks and dynamics more than the increased inputs from CO₂-stimulated photosynthesis.     

The influence of long-term fertilization on cadmium (Cd) accumulation in soil and its uptake by crops

Continuous application of organic and inorganic fertilizers can affect soil and food quality with respect to heavy metal concentrations. The risk of cadmium (Cd) contamination in a long-term (over 20 years) experimental field in North China with an annual crop rotation of winter wheat and summer maize was investigated. The long-term experiment had a complete randomized block design with seven fertilizer treatments and four replications. The seven fertilizer treatments were (1) organic compost (OM), (2) half organic compost plus half chemical fertilizer (OM?+?NPK), (3) NPK fertilizer (NPK), (4–6) chemical fertilizers without one of the major nutrients (NP, PK, and NK), and (7) an unamended control (CK). Soil samples from 0 to 20 cm were collected in 1989, 1999, and 2009 to characterize Cd and other soil properties. During the past 20 years, various extents of Cd accumulation were observed in the soil, and the accumulation was mainly affected by atmospheric dry and wet deposition and fertilization. In 2009, the average Cd concentration in the soil was 148?±?15 μg kg^?1 and decreased in the order of NPK?≈?OM?+?NKP?≈?PK?>?NP?≈?NK?>?OM?≈?CK. Sequential extraction of Cd showed that the acid-soluble fraction (F1, 32?±?7 %) and the residual fraction (F4, 31?±?5 %) were the dominant fractions of Cd in the soil, followed by the reducible fraction (F2, 22?±?5 %) and oxidizable fraction (F3, 15?±?6 %). The acid-soluble Cd fraction in the soil and Cd accumulation in the crops increased with soil plant available K. Fraction F3 was increased by soil organic C (SOC) and crop yields, but SOC reduced the uptake of soil Cd by crops. The long-term P fertilization resulted in more Cd buildup in the soil than other treatments, but the uptake of Cd by crops was inhibited by the precipitation of Cd with phosphate in the soil. Although soil Cd was slightly increased over the 20 years of intensive crop production, both soil and grain/kernel Cd concentrations were still below the national standards for environmental and food safety.     

Persistence of metsulfuron‐methyl in two soils

Abstract

The persistence of metsulfuron‐methyl in sandy loam and clay soil incubated at different temperatures and moistures contents was investigated under laboratory conditions using longbean (Vigna sesquipedalis L.) as bioassay species. A significant degradation of metsulfuron‐methyl was observed in non‐autoclaved soil rather than the autoclaved soil sample. At higher temperature, the degradation rate in non‐autoclaved soil improved with increasing soil moisture content. In non‐autoclaved sandy loam and clay soil, the half‐life was reduced from 9.0 to 5.7 and from 11.2 to 4.6 days, respectively when moisture level of sandy loam increased from 20 to 80% field capacity at 35°C. In the autoclaved soil, herbicide residue seems to have been broken down by non‐biological process. The rate of dissipation was slightly increased after the second application of the herbicide to non‐autoclaved soils but not in autoclaved soil, indicating the importance of microorganisms in the breakdown process.     

Effect of day time climatic conditions associated with different 2,4-D formulations on spray deposition and weed control

Abstract

The aim of this study was to evaluate the effect of time of the day and their associated climatic conditions on spray deposition of two 2,4-D formulations, as well as the influence on weed control. The experiment was installed in the field in complete randomized design. Treatments were arranged in factorial design 8?×?2, with 20 repetitions. First factor corresponded to different application time (1:00, 4:00, 7:00, 10:00, 13:00, 16:00, 19:00, and 22:00) with their respective climatic conditions. The second factor consisted of two formulations of 2,4-D applied at 776?g a.e. ha^?1 (2,4-D amine and 2,4-D choline salt with Colex-D? Technology) + glyphosate (816?g a.e. ha^?1). There was more spray deposition when 2,4-D choline formulation was used, and such differences were more evident for applications performed under adverse climatic conditions. More spray deposition was found in applications performed at times of day with more favorable temperature and humidity of the air conditions. Only the initial control of the evaluated species was affected by the time of application.     

The effect of temperature on the rate of disappearance of polycyclic aromatic hydrocarbons from soils

The effect of temperature on the range and rate of disappearance of four polycyclic aromatic hydrocarbons (PAHs; fluorene, anthracene, pyrene and chrysene) added as a mixture of pure compounds to two different soils (light loam and loamy sand) was investigated over 180 days in a laboratory experiment. An increase in temperature from 10 to 25 degrees C enhanced the losses of all four PAHs from both soils. The effect of temperature on the rate of PAH disappearance depended on the physico-chemical properties of the compound and of the soil. The long half-lives at lower temperatures as obtained in the laboratory tests may suggest high persistence of higher molecular weight PAHs under some field conditions.     

Transfer of cadmium, lead, and zinc from industrially contaminated soil to crop plants: a field study

The documeneed adverse health effects of soil Cd and Pb have led to public concern over soil contamination with metals. A 4-year field experiment was conducted to study the transfer of Cd, Pb, and Zn from soil contaminated by smelter flue-dust to crop plants grown in a rotation. The soil was amended with Pb?Zn smelter flue-dust (2-66.8 kg per 10 m(2) plot) to simulate the long-term effect that the smelting of non-ferrous metal ore has on arable soils. The treated soil became strongly contaminated with metals (Cd 3.2-106 mg/kg, Pb 146-3452 mg/kg, Zn 465-11 375 mg/kg). Concentrations of Cd, Pb, and Zn in barley grain, barley straw meadow bluegrass, red clover, and potatoes were generally low. The highest metal concentrations were found in potato tubers (intact), meadow bluegrass, and barley straw. The observed reduction in crop yield was probably the result of possible nutrient imbalances rather than of metal (Zn, Cu) phytotoxicities. Zn and Cd uptake by the plants can be described by the saturation (plateau) model (y = ax(b), b < 1). The relationship between Pb in the soil and plants was linear with an extremely low slope (0.0001-0.0003). No excessive dietary intake of Cd is expected when Cd concentrations in barley grain and potato tubers grown on the contaminated soil are not higher than 0.6 and 1.0 mg/kg, respectively. Based on the risk analysis and taking into account the saturation model of the soil-plant metal relationship, it was concluded that, under the conditions of this experiment (neutral soil pH), soil with Cd concentrations of up to 30 mg/kg is still safe for production of these crop plants.     

Metolachlor persistence in laboratory and field soils under Indian tropical conditions

Abstract

Metolachlor [2‐chloro‐N‐(2‐methoxy‐1‐methylethyl)‐2'‐ethyl‐6'‐methyl acetanilide] dissipation under both field and laboratory conditions were studied during summer season in an Indian soil. Metolachlor was found to have moderate persistence with a half‐life of 27 days in field. The herbicide got leached down to 15–30 cm soil layer and residues were found up to harvest day of the sunflower crop in both 0–15 cm and 15–30 cm soil layers. Metolachlor was found to be more persistent in laboratory studies conducted for 190 days. The rate of degradation was faster in soil under flooded partial anaerobic conditions as compared to aerobic soil with a half‐life of 44.3 days. In aerobic soil, metolachlor was very stable with only 49% dissipation in 130 days. Residues remained in both the soils up to the end of the experimental period of 190 days.     

Economic assessment of the negative impacts of ozone on crop yields and forest production. A case study of the estate Ostads Säteri in southwestern Sweden

Ground level ozone concentrations, in combination with the prevailing climate, at the estate Ostads S?teri in southwestern Sweden were estimated to reduce the yield of wheat and potato ranging between 5% and 10%. Occasionally, in years with the highest ozone concentrations and/or climatic conditions favoring high rates of ozone uptake to the leaves, yield loss levels above 10% may occur. Based on simple extrapolation, these ozone-induced reductions of crop yields at Ostads S?teri represent a potential total annual yield loss in Sweden in the range of 24.5 million Euro for wheat and 7.3 million Euro for potato, respectively. A simulation of forest growth at Ostad S?teri predicted that prevailing mean ozone exposure during 1993-2003 had the potential to reduce forest growth by 2.2% and the economic return of forest production by 2.6%. Using this value for extrapolation to the national level, the potential annual economic loss for Sweden due to negative impacts of ozone on forest production would be in the range of 56 million Euro (2004 prices).     

Deltamethrin degradation and effects on soil microbial activity

Deltamethrin [(S)-cyano-3-phenoxybenzyl-cis-(1R,3R)-2,2-dimethyl) cyclo–propane carboxylate),1] labelled at gem-dimethyl groups of the cyclopropane ring was applied on two Egyptian soils at a level of 10 mg/kg soil for a laboratory incubation experiment under aerobic and anaerobic conditions. A steady decrease of soil extractable¹⁴C-residues, accompanied by a corresponding increase of non- extractable bound ¹⁴C-residues was observed over a 90-day incubation period. The percentage of evolved ¹⁴CO₂ increased with time under aerobic and anaerobic conditions in both soils. The effect of deltamethrin on soil microorganisms as well as the counter effect of microorganisms on the insecticide was also investigated. As the incubation period increased, the inhibitory effect of the insecticide on the microorganisms decreased and the evolution of carbon dioxide depended on the applied dose. The nature of soil methanol soluble residues was determined by chromatographic analysis which revealed the presence of the parent insecticide as the main product in addition to four metabolites: 3-(2′,2′-dibromovinyl)-2,2-dimethylcyclopropane carboxylic acid (II); 3-phenoxybenzaldehyde (III); 3-phenoxybenzoic acid (IV); 3-phenoxybenzyl alcohol (V).     

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.     

Sorption of 1,2,4-trichlorobenzene and tetrachloroethene within an authigenic soil profile: Changes in Koc with soil depth

The sorption of 1,2,4-trichlorobenzene and tetrachloroethene was investigated in a series of well-controlled batch experiments, using authigenic soil materials from a profile extending to 2.5 m below ground surface. Batch experiment techniques were verified by study with both pulverized and unpulverized soil at different times of equilibration, using two widely different soil:water ratios, and at a wide range of aqueous concentration. Sorption isotherms were approximately linear, with sorption distribution coefficients (K_d) found to decrease roughly 100-fold down the soil profile. K_d decreased with depth to an extent greater than could be predicted on the basis of the only 10-fold decrease in natural solid organic matter (SOM) content and despite significantly higher specific surface area in the lower horizons. All base-extractable SOM in these deeper soil horizons was operationally defined as fulvic acid (FA), although there was also a significant fraction that was not extracted by the standard base technique. The lower K_d of the deeper soil horizons is believed to reflect a complex combination of (1) lower SOM content; (2) a more hydrophilic form of SOM; and (3) a more intimate association of the SOM with the mineral fraction, affecting its accessibility, sorptivity, or both. For the deeper horizons, an increase in overall K_d by more than 4-fold was observed on solids treated by either base extraction or H₂O₂ treatment, demonstrating that sorption to remaining soil components could be dramatically increased by fractional SOM removal and/or chemical alteration of the soil. A simple regression model that divides SOM into only two types (shallow and deep SOM) provides a reasonably good explanation of sorption in all seven horizons and suggests an order-of-magnitude variability in K_oc among surface soil and deeper horizons.     

Nouvelles informations relatives aux variations temporaires de l'activite nitrifiante d'un sol evaluee au laboratoire. incidences d'un apport de matieres organiques

Abstract

The results reported in this paper confirm the seasonal influence on soil nitrifying activity estimated in the laboratory. The variations of this activity depend on different factors: climatic conditions, soil nature, occurence of plants, characteristics of the organic matter added to the soil.

A fresh organic matter (straw, for example) leads to reduced nitrifying activity immediately after its incorporation; its depressive action disappears after a month under laboratory condi‐tions. A decomposed organic matter, as a manure, produces no effect.

This work also shows the seasonal variations of the mineral nitrogen immobilization after addition of a fresh organic matter.     

Sterilization affects soil organic matter chemistry and bioaccumulation of spiked p,p′-DDE and anthracene by earthworms

Laboratory experiments were conducted to assess the effects of soil sterilization on the bioavailability of spiked p,p′-DDE and anthracene to the earthworms Eisenia fetida and Lumbricus terrestris. Physical and chemical changes to soil organic matter (SOM) induced by sterilization were also studied. Uptake of both compounds added after soil was autoclaved or gamma irradiated increased for E. fetida. Sterilization had no effect on bioaccumulation of p,p′-DDE by L. terrestris, and anthracene uptake increased only in gamma-irradiated soils. Analyses by FT-IR and DSC indicate sterilization alters SOM chemistry and may reduce pollutant sorption. Chemical changes to SOM were tentatively linked to changes in bioaccumulation, although the effects were compound and species specific. Artifacts produced by sterilization could lead to inaccurate risk assessments of contaminated sites if assumptions derived from studies carried out in sterilized soil are used. Ultimately, knowledge of SOM chemistry could aid predictions of bioaccumulation of organic pollutants.     

Studies on the dissipation of 14C‐DDT from water and solid surfaces

Abstract

Dissipation of ¹⁴C‐p,p'‐DDT from water was studied for 180 days under outdoor conditions. DDT dissipated rapidly with overall half‐life of 53 days. The main degradation products were p,p'‐DDE and p,p'‐DDD. A portion of ¹⁴C‐residues was found in the sediment plus biomass (pellet) and on the inner surface of the glass container. This amounted to 7.2 and 6.7% of the initially added radioactivity, respectively. After 6 months, bound¹⁴C was more as compared to extractable ¹⁴C and p,p'‐DDD was the major metabolite of p,p'‐DDT in the extractable fraction. DDT dissipated from clay plates under indoor conditions with an overall half‐life of 160 days.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.