Development of IC-ELISA for detection of organophosphorus pesticides in water

Diethyl (carboxymethyl) phosphonate (DECP) was used as the hapten to develop an indirect competitive enzyme-linked immunosorbent assay (IC-ELISA) for detecting organophosphorus pesticides (OPs). Conjugator of DECP with bovin serum albumin (BSA) was used as the immunogen for producing the polyclonal antibodies (PcAbs). Three antisera were obtained after the immune procedure. Characterization studies of the PcAbs indicated that the titer of antiserum-1 was highest in 3 antisera, and antiserum-1 had high affinity and specificity to the parathion, dichlorvos and pirimiphos. The IC-ELISA showed an IC₅₀ of 0.428 μ g/mL with a detection limit of 0.0125 μ g/mL to parathion. The assay also indicated that the IC₅₀ values of pirimiphos and dichlorvos were 0.331 μ g/mL and 1.25 μ g/mL respectively, and the detection limits of pirimiphos and dichlorvos were 0.0116 μ g/mL and 0.048 μ g/mL respectively. Recoveries of parathion, pirimiphos and dichlorvos spiked into water samples ranged from 90% to 160%. The results indicated that the ELISA could be a convenient and supplemental analytical tool for monitoring OPs residues in environmental water samples.     

The aqueous solubility of twenty‐seven insecticides and related compounds.

Abstract

The aqueous solubilities of 27 insecticides and related compounds were determined. Diazinon, fensulfothion and paraoxon had solubilities greater than reported in the literature. The presence of impurities and/or additional components in the mixture altered the measured solubility values. Addition of acetone in amounts up to 1% (volume) produced increases in parathion solubility up to 11%. The pH values of the equilibrated solubility systems were, in most instances, acidic and, in several instances, were in the pH 3–4 range.     

Degradation kinetics of tebufenozide in model aquatic systems under controlled laboratory conditions

Abstract

The hydrolysis of the insecticide tebufenozide was studied in the dark at 20 to 40°C in buffered (pH 4 to 10) distilled water, and at 20°C in unbuffered, sterilized and unsterilized stream water. Tebufenozide was very stable in acidic and neutral buffers at 20°C and the corresponding pseudo‐first‐order rate constants (k_obsd) and half‐lives (T_1/2) were 5.946 × 10^‐4 and 13.10 × 10^‐4 d^‐1, and 1166 and 529 d, respectively. The hydrolytic degradation was dependent on pH and temperature. At pH 10 and at 20,30 and 40°C, the k_obsd (10^‐4 d^‐1) and T_1/2 (d) values were 34.22, 66.72 and 130.0; and 203, 104 and 53.3, respectively. The energy of activation (E_a) values for the hydrolysis of tebufenozide at pH 4, 7 and 10, calculated from the Arrhenius plots, were 83.50, 66.71 and 50.87 kJ/mol, respectively. Tebufenozide was stable in sterilized stream water in the dark (T_1/2 = 734 d) but it degraded fairly rapidly in unsterilized stream water (T_1/2 = 181 d). Sunlight photodegradation of the chemical was slower (T_1/2 = 83.0 h) than the photolysis by ultraviolet radiations (T_1/2 values at 254 and 365 nm were 9.92 and 27.6 h, respectively); nevertheless, it was still appreciable during the summer months at 46°31’ N latitude. The differences in degradation rates between the unsterilized and sterilized stream water and the degradation of the chemical in the sterile, distilled water in sunlight, suggests that microbial processes and photolysis are the two main degradative routes for tebufenozide in natural aquatic systems.     

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.     

Persistence of hexaconazole,a triazole fungicide in soils

Abstract

Persistence of hexaconazole (2‐(2,4‐dichlorophenyl)‐l‐(lH‐l,2,5‐triazol‐l‐yl) hexan‐2‐ol) was studied in alluvial, red and black soils under flooded and nonflooded conditions. This fungicide was more persistent in all soils under flooded conditions than under nonflooded conditions and at 27°C than at 35°C. Degradation of hexaconazole in sterilized and nonsterilized soils proceeded at identical rates indicating a minor role of micro‐organisms in its degradation. The soil persistence of hexaconazole was not affected by the addition of wheat straw both under flooded and nonflooded conditions.     

Distribution Equilibrium of Mercury (II) Chloride between Water and Air Applied to Flue Gas Scrubbing

ABSTRACT

In the literature, different values of the distribution coefficient K_H for HgCl₂ between water and air are present in a range that spans more than 3 orders of magnitude. In order to determine if a waste incineration scrubber solution could become saturated with regard to HgCl₂, an accurate experimental determination of the distribution constant of HgCl₂ at elevated temperatures is needed. In this work, the coefficient has been determined at four different temperatures between 10 and 50 °C. The Arrhenius expression obtained is 5.5 x 10⁵ x exp[-(8060 ± 2200)/7] with a corresponding enthalpy for the process HgCl₂(aq)<» HgCl₂(g) of 67 ± 20 kJ/mole. K_H at 293 K was found to be ~5 x 10^-7 atm M^-1, which is in almost perfect agreement with an earlier study. Applying the obtained K_H values to waste incineration scrubber conditions shows that no major saturation effect will occur.     

Effect of additives in the Neem formulations on deposition,volatilization and persistence of Azadirachtin in spruce foliage

Abstract

Foliar deposits, volatilization and persistence of azadirachtin‐A (AZ‐A) were investigated after application of four spray mixes prepared from a wettable powder (WP) and three emulsifiable concentrate (EC) formulations of neem. They were applied at the dosage rate of 50 g AI in 4 L/ha onto potted spruce seedlings in a laboratory spray chamber. Droplet‐size spectra and deposits were assessed using Kromekote^® card/glass plate collection units. Foliar residues [dislodgeable residues (DR), penetrated residues (PR) and total residues (TR)] of AZ‐A and their volatilization were measured by HPLC at different intervals of time up to 60 h after treatment. Differences in the droplet‐size spectra and deposit levels were observed among the four spray mixes due to the influence of additives present in them. Dissipation half‐lives (DT₅₀) of the DR, PR and TR in the foliage were low (range, 19.5 to 38.9 h) and varied according to the residue type and the spray mix used. The DT₅₀ values of the DR were consistently lower (range, 19.5 to 31.9 h) than those of the PR (range, 30.5 to 38.9 h) due to preferential loss of the surface residues. The low DT₅₀ values observed for the DR and TR in the foliage sprayed with the WP spray mix were attributed to the particulate nature of the deposit. AZ‐A volatilized appreciably from the DR rather than from the PR. The variations found in the amounts of AZ‐A volatilized (42 to 58%) and unaccountable (38 to 46%) from the initial TR values in spruce foliage, after 60 h, were attributed to the physical form of the deposits on the target surface and the influences of additives present in the different spray mixes.     

Photostabilization of the botanical insecticide azadirachtin in the presence of lecithin as UV protectant

Abstract

The phytochemical insecticide, azadirachtin (AZ), undergoes UV‐induced photodegradation. Using the isomer AZ‐A as a standard, its photochemical stability was studied with and without adding lecithin surfactant as a UV protectant. Standard solutions of pure AZ‐A and Margosan‐O^® were prepared in methanol‐hexane with (AZ‐A:lecithin, 1:2 by weight) and without lecithin, applied separately onto glass plates and maple (Acer L.) foliage and exposed to radiant energy under controlled conditions. Noticeable photostabilization of AZ‐A was achieved in the samples containing lecithin compared to AZ‐A samples without the lecithin additive. First‐order kinetic evaluation of the data showed that the DTy₅₀ (half‐life) and C (rate constant) values for AZ‐A with and without lecithin on glass plates were 5.68 d and 0.122, and 5.42 d and 0.128, respectively. The corresponding values for the Margosan‐0 formulation were 7.37 d and 0.094, and 6.24 d and 0.111. The DT₅₀ and C values for the pure AZ‐A on maple foliage with and without lecithin were 8.77 d and 0.079, and 6.54 d and 0.106, respectively. The corresponding values for the Margosan‐0 formulation on foliage were 8.35 d and 0.083, and 7.45 d and 0.093. The kinetic data gave quantitative information regarding the photostabilization of AZ‐A in the presence of lecithin. Good UV protection can only be achieved if the additive has the matching X_max of AZ‐A. The mechanism of photostabilization of AZ‐A in the presence of lecithin was due to either energy transfer from the excited AZ‐A to lecithin and/or competitive absorption of UV photons by the latter.     

Laboratory studies of dissipation of 14C‐DDT from soil and plywood surfaces

Abstract

The effects of temperature and solar radiation on dissipation of ¹⁴C‐p,p'‐DDT from a latosol soil were studied under laboratory conditions. Volatilization was measured by trapping organic volatiles during 6 weeks and was found to increase with rise of temperature from 3.8% of initial amount at ambient temperature to 5.9% at 45°C.

Studies on the effect of solar radiation using quartz tubes under sterilized and non‐sterilized conditions have shown that volatilized organics were highest in quartz tubes, with soil microflora presumably playing a very minor role in volatilization. Mineralization was shown to be low in sterilized systems and highest in non‐sterilized quartz systems. Studies on binding suggest that soil bioactivity may be involved in the formation of a portion of the bound residue. These laboratory experiments seem to support data from the field, where it is maintained that volatilization is a major mechanism for dissipation. Degradation in soil and to a lesser extent solar irradiation contribute also substantially to the dissipation mechanisms. Radiocarbon dissipated from plywood surfaces under indoor conditions in a biphasic fashion. Loss of 50% occurred after 5.5 weeks while the remainder dissipated at a very slow rate.     

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.     

Development of IC-ELISA for detection of organophosphorus pesticides in water

Diethyl (carboxymethyl) phosphonate (DECP) was used as the hapten to develop an indirect competitive enzyme-linked immunosorbent assay (IC-ELISA) for detecting organophosphorus pesticides (OPs). Conjugator of DECP with bovin serum albumin (BSA) was used as the immunogen for producing the polyclonal antibodies (PcAbs). Three antisera were obtained after the immune procedure. Characterization studies of the PcAbs indicated that the titer of antiserum-1 was highest in 3 antisera, and antiserum-1 had high affinity and specificity to the parathion, dichlorvos and pirimiphos. The IC-ELISA showed an IC50 of 0.428 micro g/mL with a detection limit of 0.0125 micro g/mL to parathion. The assay also indicated that the IC50 values of pirimiphos and dichlorvos were 0.331 micro g/mL and 1.25 micro g/mL respectively, and the detection limits of pirimiphos and dichlorvos were 0.0116 micro g/mL and 0.048 micro g/mL respectively. Recoveries of parathion, pirimiphos and dichlorvos spiked into water samples ranged from 90% to 160%. The results indicated that the ELISA could be a convenient and supplemental analytical tool for monitoring OPs residues in environmental water samples.     

Droplet size spectra and deposits of two aerially sprayed Bacillus thuringiensis formulations on artificial samplers and live foliage

Abstract

Two commercial formulations of Bacillus thuringiensis var. kurstaki (BTK), Foray^® 48B and Thuricide^® 48LV, were applied aerially over nine spray blocks in a hardwood forest in West Virginia in 1991. Droplet spectra and spray mass deposits were determined using water‐sensitive paper strips (WSPS), glass micro‐fiber filters (GMFFs), glass plates and castor oil. Mass deposits of BTK were also assessed on natural foliage by two bioassay methods, i.e., feeding of homogenized foliage containing a starch‐sucrose solution and force‐feeding bioassay of foliar extracts containing re‐dissolved protein precipitate. Deposits on canopy foliage and ground samplers were also assessed by total protein assay and enzyme‐linked immunosorbent assay (ELISA). Droplet spectra on the WSPS were different from those on castor oil. Droplets on horizontal ground WSPS were larger than those on vertical ground WSPS. WSPS placed at canopy level collected more droplets than those at ground level. The total protein deposits (ng/cm²) were consistently higher on all blocks than the delta‐endotoxin protein deposits. Spray mass recovery on the ground samplers were low, and ranged from 2.9 to 8.0% of the applied rates.     

Attractancy evaluation of ceralure‐B1 isomer via field captures of mediterranean fruit flies (Diptera: Tephritidae)

Abstract

Commercially prepared ceralure‐B1, an attractant for the Mediterranean fruit fly, Ceratitis capitata (Wiedemann) (Diptera: Tephritidae), was evaluated in trapping tests by comparison with commercial ceralure and trimedlure. Jackson traps were used for medfly captures. The residual ceralure‐B1, ceralure, and trimedlure contents of aged dispensers were determined. The results of this study show that male medfly captures from traps with ceralure‐B1 were as high or higher than male medfly captures from traps with twice the quantity of ceralure or trimedlure. The use of regioselectively synthesized ceralure‐B1, enriched in B1, as a source of a more potent attractant than commercial ceralure and as a more persistent male medfly attractant than trimedlure is reported.     

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.     

Appendix

Abstract

The interaction of glyphosate [N‐(phosphonomethyl)‐glycine] with four typical European soils is reported. Results of adsorption and desorption isotherms show that the interaction of glyphosate with these soils was mainly related to content of iron and aluminium amorphus hydroxides. Moreover, it was found that the presence of divalent cations in 2: 1 clay minerals also contribute to glyphosate adsorption. The S‐type form of the adsorption isotherms revealed the existence of two different binding sites. These were exchangeable cations at low herbicide concentration and Fe and Al at higher glyphosate concentrations. The K maximum values of adsorption provided by the linear form of the Langmuir equation were found to be more consistent with soil parameters than those calculated by the Freundlich equation. The order of desorption from the soils was the reverse of that found for adsorption. Moreover, desorption varied from around 15 to 80% of the adsorbed herbicide according to the soil characteristics. This indicated that glyphosate adsorption on soils is far from being permanent and leaching to lower soil horizons with limited biological activity may occur.     

The electron density distribution in pyridinium and bipyridylium compounds and its relevance to their adsorption by expanding lattice clays

Abstract

Charge distributions in 1, 1'‐ethylene‐2, 2'‐bipyridylium (diquat), 1,1'‐dimethyl‐4,4'‐bipyridylium (paraquat) and 1‐methylpyridinium organocations were calculated by a Complete Neglect of Differential Overlap semi‐empirical quantum mechanical procedure. The data show that the positive charges in the organocations are distributed around the molecules and are greatest in the positions ortho and para to the heterocyclic nitrogen atoms. Earlier interpretations of the mechanisms of adsorption of paraquat and diquat by soils and clays assumed that the charges were located in the heterocyclic nitrogen atoms. Here some consideration is given to the influence of the charge delocalizations on the processes of adsorption by montmorillonite and vermiculite clay preparations.     

Removal of 2, 4‐D from aqueous solution by the adsorbents from spent bleaching earth

Abstract

The removal of 2, 4‐D (2, 4‐ dichlorophenoxyacetic acid) from aqueous solutions by activated spent bleaching earths (SBE) was studied at 20 °C. Experiments were performed as a function of time, initial concentration, dose and particle size of the adsorbent. The Langmuir and Freundlich adsorption equations were fitted by the adsorption data obtained. The values of Langmuir and Freundlich constants were determined. The adsorption kinetic was found to follow Lagergren equation. Both the boundary layer and intraparticle diffusion played important roles in the adsorption rate of 2, 4‐D. As the size of the adsorbent increased, the time to reach equilibrium increased but adsorption capacity decreased.     

Studies of the effects of temperatures and solar radiation on volatilization,mineralization and binding of 14c‐DDT in soil under laboratory conditions

Abstract

The effects of temperatures and solar radiation on the dissipation of ¹⁴C‐p,p'‐DDT from a loam soil was studied by quantifying volatilization, mineralization and binding. The major DDT loss occurred by volatilization, which was 1.8 times more at 45^oC than at ambient temperature (30°C). Mineralization of DDT slowly increased with time but it decreased slightly with increase in temperature. Binding of DDT to soil was found to be less at higher temperatures (35 and 45°C) as compared to ambient temperature. Degradation of DDT to DDE was faster at higher temperatures.

Exposure of non‐sterilized and sterilized soils treated with ¹⁴C‐DDT to sunlight in quartz and dark tubes for 6 weeks resulted in significant losses. Volatilization and mineralization in quartz tubes were more as compared to dark tubes. The volatilized organics from the quartz tubes contained larger amounts of p,p'‐DDE than the dark tubes. Further, higher rates of volatilization were found in non‐sterilized soils than in sterilized soils. The results suggest that faster dissipation of DDT from soil under local conditions relates predominantly to increased volatilization as influenced by high temperature and intense solar radiation.     

Ultrasonic decomposition of atrazine and alachlor in water.

Abstract

The collapse of ultrasonically‐generated cavitation bubbles can result in sonochemical reactions. The kinetics of sonochemical decomposition of alachlor and atrazine in water were determined using a sonicator operating in the continuous mode at maximum output. Alachlor and atrazine solutions, 3.1 nmol L^‐1, were kept at constant temperature during the sonication. Decomposition at 30°C followed first‐order kinetics: k = 8.01 × 10^‐3 min^‐1 and 2.10 × 10^‐3 min^‐1 for alachlor and atrazine, respectively. It is not clear from the product analysis whether the decomposition was due to a thermal or free radical reaction. However, regardless of the decomposition mechanisms, the extrapolated half‐lives (86 and 330 min for alachlor and atrazine, respectively) support the potential development of ultrasonic waves to decompose herbicides in contaminated water.