Spatial distribution of hexazinone and metabolites in a luvisolic soil

Abstract

The spatial distribution of hexazinone and two primary metabolites were measured in forest soil for two years following the aerial application of a granular formulation, PRONONE 10G, in northern Alberta. Residues were quantified using solid‐phase extraction and capillary gas chromatography. Initial deposition rates of two hexazinone treatments averaged 2.3 ± 0.5 and 4.1 ± 0.8 kg/ha for each triplicated plots. One year after application, residues of hexazinone averaged 0.25 ± 0.09 and 0.40 ± 0.02 kg/ha in 2.3 and 4.1 kg/ha treatment, respectively, in the 0–10 cm surface soil; and were distributed vertically in soil depths of 0–10, 10–20, and 20–30 cm at ratios of 10:11:2 and 10:5:2, respectively, in 2.3 and 4.1 kg/ha treatment. Metabolites A and B amounted to 15 and 30% of hexazinone, respectively. Two years after application, the vertical movement of hexazinone in soil was quantifiable to the 40‐cm depth in both 2.3‐ and 4.1‐kg/ha treatment plots. Trace amounts of hexazinone were detected at 130 cm only in the 2.3‐kg/ha plot, which is likely due to the more freely downward movement of hexazinone to deeper horizons along decayed root channels.     

Bioavailability and dissipation of fluridone under controlled conditions

Abstract

Bioavailability of fluridone, l‐methyl‐3‐phenyl‐5‐[3‐(trifluoromethyl) phenyl]‐4(1H)‐pyridinone, as affected by soil temperature, soil moisture regime, and duration of incubation was investigated in three soil types by grain sorghum (Sorghum bicolor [L.] Moench cv. Abu Sabien) chlorophyll bioassay. Initial loss of fluridone was rapid and dissipation followed first‐order kinetics under most of the incubation treatments investigated. Soil moisture, in general, had a greater impact than soil temperature on dissipation of fluridone. The herbicide dissipated faster at the fluctuating room temperature (18–24°C) than at the constant 10°C in Sonning sandy clay loam (O.M. = 1.2%) and Erl Wood sandy loam (O.M. = 2.5%) but not in Shropshire loamy peat (O.M. = 33%). In the two mineral soils, bioassay‐detectable residues from an initial rate of 1.00 μg/g were least (0.00 ‐ 0.10 μg/g) at 1/2 field capacity (FC) and greatest (0.16 ‐ 0.37 μg/g) at 1/4 FC, 400 days after treatment. At 10°C, the DT₅₀ values (days) at 1/4 FC and 1/2 FC were, respectively, 147 ± 16 and 69 ± 6 for Erl Wood soil, and 257 ± 28 and 51 ± 12 for Sonning soil. In Shropshire soil, concentrations of bioavailable fluridone were least at each bioassay date when soil moisture was maintained at FC, at both temperatures of incubation. At 10°C, herbicide concentrations in the organic soil from an initial rate of 10.00 μg/g were 0.95 and 4.69 μg/g, respectively, at FC and 1/4 FC.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

Comparison of Outdoor and Classroom Ozone Exposures for School Children in Mexico City

Abstract

To evaluate methods of reducing exposure of school children in southwest Mexico City to ambient ozone, outdoor ozone levels were compared to indoor levels under three distinct classroom conditions: windows/doors open, air cleaner off; windows/doors closed, air cleaner off; windows/ doors closed, air cleaner on. Repeated two-minute average measurements of ozone were made within five minutes of each other inside and outside of six different school classrooms while children were in the room. Outdoor ozone two-minute average levels varied between 64 and 361 ppb; mean outdoor levels were above 160 ppb for each of the three conditions. Adjusting for outdoor relative humidity, for a mean outdoor ozone concentration of 170 ppb, the mean predicted indoor ozone concentrations were 125.3 (±5.7) ppb with windows/doors open; 35.4 (±4.6) ppb with windows/ doors closed, air cleaner off; and 28.9 (±4.3) ppb with windows/ doors closed, air cleaner on. The mean predicted ratios of indoor to outdoor ozone concentrations were 0.71 (±0.03) with windows/doors open; 0.18 (±0.02) ppb with windows/doors closed, air cleaner off; and 0.15 (±0.02) ppb with windows/doors closed, air cleaner on. As outdoor ozone concentrations increased, indoor ozone concentrations increased more rapidly with windows and doors open than with windows and doors closed. Ozone exposure in Mexican schools may be significantly reduced, and can usually be kept below the World Health Organization (WHO) guideline of 80 ppb, by closing windows and doors even when ambient ozone levels reach 30Q ppb or more.     

Behaviour of DDT under laboratory and outdoor conditions in Germany

Abstract

Experiments were conducted on adsorption, volatilization and UV‐degradation of p,p'‐DDT on soil surface, and leaching and degradation in sand columns. p,p'‐DDT was shown to adsorb stronger to soils with higher organic content. UV irradiation at 290 nm for 10 hours mineralized less than 0.1% of DDT in soil.

Results show that only 0.1% of DDT volatilized in a sun‐exposed semi‐closed quartz system. Polar compounds accounted from 1.4% after 55 days. The rate of volatilization and degradation in an open system was much higher; only 15% DDT and 7% DDE were recovered after 6 weeks in the organic extract. p,p'‐DDT was adsorbed to a great extent on the top layers of sand columns; 86% in the top 8 cm.     

Determination of disulfoton and permethrin residues in an organic soil and their translocation into lettuce,onion and carrot 1

Abstract

The residues of disulfoton and permethrin in an organic soil and in vegetables grown in soil treated with a granular formulation of the pesticides were determined by gas chromatography. The residues were removed from soil or plant samples by successive extractions with acetone and hexane. Permethrin persisted in the soil for the initial 28 days and declined slowly during the rest of the season but disulfoton after persisting for one week at the applied concentration was degraded in the next two weeks. The insecticides did not translocate into the edible parts of the vegetables but were present in the root system of onion and lettuce. Carrot and lettuce yields were not significantly different from those of the controls but onion yields were substantially decreased by the use of per‐methrin.     

Comparative hersistence of chlorpyrifos in a mineral soil after granular and drench applications

Abstract

Lorsban 15G (15% chlorpyrifos) at 1.6 and 2.2 g a.i./10 m row, and Lorsban 4E (40.7% chlorpyrifos) at 2.0 g a.i./10 m row were applied respectively to a silt loam soil as a band treatment at seeding and as a drench after seeding. The rate of disappearance of chlorpyrifos [Q,Q‐diethyl Q‐(3,5,6‐trichloro‐2‐pyridinyl) phosphorothioate] was relatively fast in the first 15 days but slowed down considerably thereafter regardless of the methods of application and application rates; and there was a statistically significant (p=0.05) linear relationship between the natural logarithm of chlopyrifos concentration and time. Based on the linear regression equations, the calculated pseudo‐first‐order rate constants were 0.041 day^‐1 and 0.044 day^‐1 respectively for the band treatments at 1.6 and 2.2 g a.i./10 m row; and 0.040 day^‐1 for the drench. The calculated half‐lives for all three treatments were similar and they ranged frcm 15.8 days to 17.3 days. The degradation product 3,5,6‐trichloro‐2‐pyridinol (TP) was detected in soil but not 3,5_/6‐trichloro‐2‐methoxypyridine (TMP). The concentration of TP increased steadily to a peak and declined thereafter. The highest mean concentration of TP was 2.21 ppm (dry wt) detected 29 days after band treatment at the high rate. After 90 days the concentration of TP decreased to 0.43 ppm (dry wt).     

Layer of organic pine forest soil on top of chlorophenol-contaminated mineral soil enhances contaminant degradation

Chlorophenols, like many other synthetic compounds, are persistent problem in industrial areas. These compounds are easily degraded in certain natural environments where the top soil is organic. Some studies suggest that mineral soil contaminated with organic compounds is rapidly remediated if it is mixed with organic soil. We hypothesized that organic soil with a high degradation capacity even on top of the contaminated mineral soil enhances degradation of recalcitrant chlorophenols in the mineral soil below. We first compared chlorophenol degradation in different soils by spiking pristine and pentachlorophenol-contaminated soils with 2,4,6-trichlorophenol in 10-L buckets. In other experiments, we covered contaminated mineral soil with organic pine forest soil. We also monitored in situ degradation on an old sawmill site where mineral soil was either left intact or covered with organic pine forest soil. 2,4,6-Trichlorophenol was rapidly degraded in organic pine forest soil, but the degradation was slower in other soils. If a thin layer of the pine forest humus was added on top of mineral sawmill soil, the original chlorophenol concentrations (high, ca. 70 μg g^?1, or moderate, ca. 20 μg g^?1) in sawmill soil decreased by >40 % in 24 days. No degradation was noticed if the mineral soil was kept bare or if the covering humus soil layer was sterilized beforehand. Our results suggest that covering mineral soil with an organic soil layer is an efficient way to remediate recalcitrant chlorophenol contamination in mineral soils. The results of the field experiment are promising.     

Sorption of chlorpyrifos and fonofos on four soils and turfgrass thatch using membrane filters

Abstract

Chemical transport in soil is a major factor influencing soil and water contamination. Four soils and turfgrass thatch, representing a wide range of organic carbon OC content were studied to determine sorption K_d and K_f parameters for the insecticides chlorpyrifos and fonofos. The batch equilibrium method was used. The concentration of insecticide was measured in the solution as well as in the solid phase to determine the most accurate sorption data. Four soils and thatch were equilibrated for 24 h at 22 ± 1^OC with aqueous insecticide solutions. Four concentrations of the insecticides, each <50% of their respective water solubilities, were selected for the experiments. After extraction with an organic solvent, the concentration of insecticides in the aqueous solution was determined by gas liquid chromatography using electron capture detection for chlorpyrifos, and nitrogen/phosphorus detection for fonofos. Data obtained were fitted to the log and simple linear form of the Freundlich equation. Mass balance Freundlich isotherm exponents n ranged between 0.82 and 0.93 for chlorpyrifos. 0.82 and 1.21 for fonofos, with r² ≥ 0.97. K_oc (percent of organic carbon %OC normalized Sorption coefficient) values were calculated by using experimentally developed K_d and K_f coefficients in relation to OC levels from 0.29 to 34.85%. K_d and K_f coefficients of both insecticides were positively correlated with OC (r² ≥ 0.96). organic matter OM (r² ≥ 0.96), and cation exchange capacity CEC (r² ≥ 0.90).     

Degradation of chlorpyrifos and its hydrolysis product, 3,5,6‐trichloro‐2‐pyridinol,in soil

Abstract

The degradation of ¹⁴C‐chlorpyrifos and its hydrolysis product, 3,5,6‐trichloro‐2‐pyridinol (TCP), was investigated in soil in laboratory experiments. Between 12 and 57% of the applied chlorpyrifos persisted in a variety of agricultural soils after a 4‐week incubation. Concentrations of TCP present in these soils ranged from 1 to 34% of the applied dose. Two patterns of persistence were observed. In some soils, significant quantities of TCP and soil‐bound residues were produced, but little ¹⁴CO₂. In other soils, neither TCP nor soil‐bound residues accumulated, but large quantities of ¹⁴CO₂ were evolved. Direct treatment of fresh samples of each of these soils with ¹⁴C‐TCP resulted in rapid mineralization of TCP to ¹⁴CO₂ only in those soils in which TCP had not accumulated after chlorpyrifos treatment. The rapid mineralization of TCP in these soils was microbially mediated, but populations of soil microorganisms capable of using TCP as a sole carbon‐energy source were not detected.     

Comparison and Evaluation of Chemically Speciated Mobile Source PM2.5 Particulate Matter Profiles

ABSTRACT

Mobile sources are significant contributors to ambient PM_{2 5}, accounting for 50% or more of the total observed levels in some locations. One of the important methods for resolving the mobile source contribution is through chemical mass balance (CMB) receptor modeling. CMB requires chemically speciated source profiles with known uncertainty to ensure accurate source contribution estimates. Mobile source PM profiles are available from various sources and are generally in the form of weight fraction by chemical species. The weight fraction format is commonly used, since it is required for input into the CMB receptor model. This paper examines the similarities and differences in mobile source PM_2.5 profiles that contain data for elements, ions, elemental carbon (EC) and organic carbon (OC), and in some cases speciated organics (e.g., polycyclic aromatic hydrocarbons [PAHs]), drawn from four different sources.

Notable characteristics of the mass fraction data include variability (relative contributions of elements and ions) among supposedly similar sources and a wide range of average EC:OC ratios (0.60 ± 0.53 to 1.42 ± 2.99) for light-duty gasoline vehicles (LDGVs), indicating significant EC emissions from LDGVs in some cases. For diesel vehicles, average EC:OC ratios range from 1.09 ± 2.66 to 3.54 ± 3.07. That different populations of the same class of emitters can show considerable variability suggests caution should be exercised when selecting and using profiles in source apportionment studies.     

Fenvalerate concentrations in a mineral and an organic soil receiving multiple applications during the growing season

Abstract

Fenvalerate EC at 140 g AI/ha was applied 7 times at 2 wk intervals to duplicate plots of Plainfield sand and an organic soil contained in 2.2 x 0.9 m field microplots with and without an onion crop present in 1980 and 1981 respectively. Soil samples were taken immediately before and after each application and at 2, 4, and 6 wk after the last application in 1980. Additional samples were taken at 22 and 34 wk for the 1981 treatment. Concentrations of fenvalerate were determined by glc. In the crop‐free mineral soil, fenvalerate levels declined from. 0.07–0.11 ppm immediately after spraying to 0.01–0.03 ppm after 2 wk; in the organic soil the rate of addition of fenvalerate exceeded the rate of disappearance and the concentration in the soil gradually increased over the 14 wk treatment period to the 0.9–1.0 ppm range. This concentration decreased slowly over the next 10 wk to 0.7–0.8 ppm and was still 0.5–0.7 ppm the following spring. Results were similar for cropped soils. Concentrations in the top third of the 15 cm cores were 6x and 15x those in the middle third for sand and organic soil, respectively. Concentrations, in the onions at harvest were <0.01 ppm.     

Sorption and photodegradation of chlorpyrifos on riparian and aquatic macrophytes

Surface water bodies may become contaminated via spray drift following pesticide application. In this investigation, the photodegradation and sorption of chlorpyrifos was studied in four riparian macrophytes representative of Mediterranean flora (Phragmites australis, Iris pseudacorus, Equisetum pratense and Typha latifolia). The results of experiments with both the active ingredient and the formulation DURSBAN 48® EC confirm the ability of these species to interact with chemicals such as chlorpyrifos. The maximum sorption of chlorpyrifos at equilibrium was observed in Phragmites australis (22%). And, the maximum instantaneous sorption of chlorpyrifos was observed in the dried biomass of Phragmites australis (49%). The epicuticular waxes present on leaves influence photodegradation processes, resulting in a decrease in chlorpyrifos persistence depending on the nature of the extract. The half-life of chlorpyrifos residues in leaf waxes decreased from 34 to 99 minutes when irradiated.     

Modifications to the Sunset Laboratory Carbon Aerosol Monitor for the Simultaneous Measurement of PM2.5 Nonvolatile and Semi-Volatile Carbonaceous Material

Abstract

Semi-volatile organic carbonaceous material (SVOC) in fine particles is not reliably measured with conventional semicontinuous carbon monitors because semi-volatile carbonaceous material is lost from the collection media during sample collection. Two modifications of a Sunset Laboratory carbon aerosol monitor allowing for the determination of semi-volatile fine particulate organic material are described. Collocated conventional and modified instruments were operated simultaneously using a common inlet. Comparisons were made with integrated PC-BOSS data for quartz filter retained nonvolatile organic carbon (NVOC) and elemental carbon (EC), SVOC, and total carbon (TC = SVOC + NVOC + EC) and good agreement was observed between TC concentrations during studies conducted in Rubidoux, CA. Precision of the comparison was σ=±1.5 μg-C/m³ (±8%). On the basis of experiments performed with the modified Sunset monitor, a dual-oven Sunset monitor was developed and extensively tested in Lindon, UT; Riverside, CA; and in environmental exposure chambers. The precision for the measurement of TC with the dual-oven instrument was σ = ±1.4 μg-C/m³ (±13%).     

Phytoavailability and extractability of potassium,magnesium and manganese in calcareous soil amended with olive oil wastewater

Abstract

Land disposal of olive oil wastewater using it as a soil amendment requires a knowledge of the effects that its application may produce on the status of the mineral nutrients in the plant‐soil system. A pot experiment using calcareous soil was performed in a growth chamber to examine the effects of olive oil wastewater on the availability and postharvest soil extractability of K, Mg and Mn. The experiment included 6 treatments: two rates of olive oil wastewater, two mineral fertilizer treatments containing K (which supplied K in amounts equivalent to the K supplied by the olive oil wastewater treatments), a K‐free mineral fertilizer treatment, and a control. The pots were sown with ryegrass as the test plant, harvesting 3 times at intervals of one month. Olive oil wastewater has demonstrated a considerable capacity for supplying K that can be assimilated by the plant, tending in fact to surpass the mineral potassium fertilizer tested. The application of olive oil wastewater tends to reduce the concentration of Mg in the plant, similarly to the effect of adding mineral potassium fertilizer. An enhancement of Mn availability takes place in the soil amended with olive oil wastewater, which on occasion has produced Mn concentrations in plant that could be considered phytotoxic or at least excessive. After harvesting, we observed an increase in the amount of exchangeable K in soil with added industrial wastewater. However, these increases are lower than those in soil treated with mineral potassium fertilizer. The levels of exchangeable, carbonate‐bound, organic‐bound and residual Mg in soil were higher in treatments incorporating olive oil wastewater than in those with added mineral K, with the opposite tendency occurring in the amount of Fe‐Mn oxides‐bound Mg in soil. Treatments based on olive oil wastewater, especially in high doses, increased the amount of exchangeable and carbonate‐bound Mn in soil, in comparison with treatments adding mineral fertilizers with or without K. In contrast, the addition of industrial wastewater caused a drop in the amount of Fe‐Mn oxides‐bound and organic‐bound Mn in soil.     

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.     

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.     

Persistence of azadirachtin A and B in soil: Effects of temperature and microbial activity

Abstract

The persistence of two insecticidally active compounds from the neem tree, azadirachtin A and B, was determined at two different temperatures (15 and 25°C) in the laboratory after application of the commercial neem insecticide, Margosan‐O, to a sandy loam soil. The influence of microbial activity on degradation was also examined by comparing autoclaved and non‐autoclaved soils also at 15 and 25°C. Temperature influenced degradation rates. The DT ₅₀ (time required for 50% disappearance of the initial concentration) for azadirachtin A was 43.9 and 19.8 d for non‐autoclaved soil kept at 15 and 25°C, respectively. The DT ₅₀ for azadirachtin B was 59.2 and 20.8 d for non‐autoclaved soil kept at 15 and 25°C, respectively. Microbial activity was also responsible for faster degradation because DT ₅₀ ’s for autoclaved soil were much longer than for non‐autoclaved soils. DT ₅₀ ‘_s for azadirachtin A in autoclaved soil were 91.2 (15°C) and 31.5 d (25°C). DT50’s for azadirachtin B in autoclaved soil were 115.5 (15°C) and 42.3 d (25°C). Two degradation products of azadirachtin were detected, but were not identified. Higher levels of the two degradation products were detected in non‐autoclaved soil.     

Dissipation of chlorpyrifos,oxon, and 3,5,6‐trichloro‐2‐pyridinol in litter and elm forest soil

Abstract

After chlorpyrifos was applied to the basal 1 meter of elm tree trunks for control of elm bark beetles at two different application times and sites, initial chlorpyrifos residues in forest floor litter ranged from 120 to 916 μg/g depending on the application time. Residues dissipated by approximately 99% after 791 d with the DT₅₀ from 3.9 to 59 d and DT₉₀ from 55 to 310 d. The initial residues of chlorpyrifos in elm forest soil varied from 0.8 to 28 μg/g and were 1 to 2 μg/g at 791 d after application. The dissipation half‐lives of chlorpyrifos in fortified soil placed in the field ranged from 116 to 121 d.     

Effect of four experimental insecticides on enzyme activities and levels of adenosine triphosphate in mineral and organic soils

Abstract

A laboratory study was conducted to determine the effect of four experimental insecticides, DOWCO429X, DPX43898, tefluthrin and trimethacarb, on enzyme activities and levels of adenosine 5'‐triphosphate (ATP) in mineral and organic soils. DOWCO429X decreased urease activity in organic soil after 7 days while a stimulatory effect was observed with most treatments after 14 days. No inhibition on acetylene (C₂H₂) reduction by nitrogenase was evident with any of the insecticides in either soil. With the exception of DOWCO429X and tefluthrin at 7 days in organic soil, none of the insecticide treatments inhibited dehydrogenase activity in either soil. Dehydrogenase activity, measured by formazan formation, was greater in many samples in sandy loam than the control throughout the experiment. No inhibitory effect was observed on amylase activity after 2 or 3 days in sandy soil. A stimulatory effect was apparent in many samples after 2 days in organic soil. All insecticide treatments in sandy soil reduced invertase activity at 2 days. However, none of the experimental insecticides inhibited invertase activity after 3 days. A stimulatory effect in invertase activity was apparent in most cases at 2 days in organic soil and no difference was observed after 3 days. Phosphatase activity in insecticide treated samples was equal to or greater than that of control in sandy soil after 2 h. With the exception of DPX43898, the insecticides depressed phosphatase activity in most organic soil samples. The insecticides did not affect ATP levels in either soil. Results indicated that the chemical treatments at the levels tested did not significantly affect activities of enzymes or level of ATP in both soils.