Development of an analytical method for analysis of flubendiamide,des-iodo flubendiamide and study of their residue persistence in tomato and soil

Flubendiamide is a new insecticide that has been found to give excellent control of lepidopterous pests of tomato. This study has been undertaken to develop an improved method for analysis of flubendiamide and its metabolite des-iodo flubendiamide and determine residue retention in tomato and soil. The analytical method developed involved extraction of flubendiamide and its metabolite des-iodo flubendiamide with acetonitrile, liquid-liquid partitioning into hexane-ethyl acetate mixture (6:4, v v^?1) and cleanup with activated neutral alumina. Finally the residues were dissolved in gradient high pressure liquid chromatography (HPLC) grade acetonitrile for analysis by HPLC. The mobile phase, acetonitrile-water at 60:40 (v v^?1) proportion and the wavelength of 235 nm gave maximum peak resolution. Using the above method and HPLC parameters described, nearly 100 % recovery of both insecticides were obtained. There was no matrix interference and the limit of quantification (LOQ) of the method was 0.01 mg kg^?1. Initial residue deposits of flubendiamide on field-treated tomato from treatments @ 48 and 96 g active ingredient hectare^?1 were 0.83 and 1.68 mg kg^?1,respectively. The residues of flubendiamide dissipated at the half-life of 3.9 and 4.4 days from treatments @ 48 and 96 g a.i. ha^?1, respectively and persisted for 15 days from both the treatments. Des-iodo flubendiamide was not detected in tomato fruits at any time during the study period. Residues of flubendiamide and des-iodo flubendiamide in soil from treatment @ 48 and 96 g a.i. ha^?1 were below detectable level (BDL, < 0.01 mg kg^?1) after 20 days. Flubendiamide completely dissipated from tomato within 20 days when the 480 SC formulation was applied at doses recommended for protection against lepidopterous pests.     

PM2.5 source apportionment with organic markers in the Southeastern Aerosol Research and Characterization (SEARCH) study

Positive matrix factorization (PMF) and effective variance (EV) solutions to the chemical mass balance (CMB) were applied to PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) mass and chemically speciated measurements for samples taken from 2008 to 2010 at the Atlanta, Georgia, and Birmingham, Alabama, sites. Commonly measured PM_2.5 mass, elemental, ionic, and thermal carbon fraction concentrations were supplemented with detailed nonpolar organic speciation by thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). Source contribution estimates were calculated for motor vehicle exhaust, biomass burning, cooking, coal-fired power plants, road dust, vegetative detritus, and secondary sulfates and nitrates for Atlanta. Similar sources were found for Birmingham, with the addition of an industrial source and the separation of biomass burning into open burning and residential wood combustion. EV-CMB results based on conventional species were qualitatively similar to those estimated by PMF-CMB. Secondary ammonium sulfate was the largest contributor, accounting for 27–38% of PM_2.5, followed by biomass burning (21–24%) and motor vehicle exhaust (9–24%) at both sites, with 4–6% of PM_2.5 attributed to coal-fired power plants by EV-CMB. Including organic compounds in the EV-CMB reduced the motor vehicle exhaust and biomass burning contributions at both sites, with a 13–23% deficit for PM_2.5 mass. The PMF-CMB solution showed mixing of sources within the derived factors, both with and without the addition of speciated organics, as is often the case with complex source mixtures such as those at these urban-scale sites. The nonpolar TD-GC/MS compounds can be obtained from existing filter samples and are a useful complement to the elements, ions, and carbon fractions. However, they should be supplemented with other methods, such as TD-GC/MS on derivitized samples, to obtain a wider range of polar compounds such as sterols, sugars, and organic acids. The PMF and EV solutions to the CMB equations are complementary to, rather than replacements for, each other, as comparisons of their results reveal uncertainties that are not otherwise evident.

Implications:?Organic markers can be measured on currently acquired PM_2.5 filter samples by thermal methods. These markers can complement element, ion, and carbon fraction measurements from long-term speciation networks. Applying the positive matrix factorization and effective variance solutions for the chemical mass balance equations provides useful information on the accuracy of the source contribution estimates. Nonpolar compounds need to be complemented with polar compounds to better apportion cooking and secondary organic aerosol contributors.     

Leaching of mecoprop and dichlorprop in calcareous soil. Effect of the exogen organic matter addition in this process

Abstract

Leaching studies of mecorprop (R,S)‐2‐(4‐chloro‐2‐methylphenoxy)propanoic acid, and dichlorprop, (R,S)‐2‐(4‐chloro‐2,4‐dichlorophenoxy) propanoic acid, under saturated conditions were conducted in unamended and amended soil columns. The purpose of the study was to investigate the leaching of these herbicides in three type of soils and the exogen organic matter effect on this process. The leaching patterns could be related to variation in the soil texture and diffusion processes of the herbicides into micropores within the walls of conducting pore. The leaching rate in the amended soil columns decreased with the addition of organic matter. The breakthrough curves (BTC) of these herbicides in the leachates of the amended soil columns were wider and more diffused than the BTC obtained for the corresponding unamended soil. The theoretical BTC overestimated the pore volume required for the displacement of these pesticides from the soil column. This may be due to the differences in the adsorption process between the bacth and soil columns methods     

Determination of organochlorine and organophosphate pesticide residues in fruits,vegetables and sediments

Abstract

A method is described for the determination of organochlorine and organophosphate pesticide residues in fruits, vegetables and sediments. The concentrated solvent extract was sealed in a polymeric membrane tube, dialysed in cyclohexane and the solvent replaced with hexane. The organophosphates were analysed on a specific thermionic detector without further clean‐up. For the organochlorine pesticides the extract was eluted through 3 g of alumina and analysed on GC/ECD. The clean‐up for sediment extract was carried out on a10 g alumina column with 100 mL hexane containing 5% acetone and the eluate was concentrated to 5 mL.

The detection limit for organophosphates on a 40 g sample and a final volume of 10 mL was on the average 0.01 mg/kg. The detection limit for organochlorine pesticides, with the final volume of 25 mL, was 0.005 mg/kg for all pesticides except for p,p'‐DDT and endosulfan sulphate, which was 0.01 mg/kg.

The detection limit for oganochlorine pesticides in sediment, with the final volume of 2 mL, was less than 1 μg/kg and for organophosphate pesticides less than 10 μg/kg when the final volume was made to 0.5 mL. At the detection limits the method produced a very high coefficient of variation for both organochlorine and organophosphate pesticides.     

Eliminating Reheat from Existing FGD Systems

The Clean Air Act Amendments of the early 1970_s required coal burning utilities to reduce their emissions of sulfur dioxide. Lime or limestone based wet systems were employed for flue gas desulfurization (FGD). These systems reduced flue gas temperatures to below acid dew point conditions. Concerned about the prospect of ductwork exposed to a saturated, acid-rich environment, most utilities turned to stack gas reheat (SGR) to increase flue gas temperatures. By 1980, 82 percent of all FGD facilities employed SGR. Today there are about 130 FGD systems of which 101 employ some form of stack gas reheat.     

Technical Session Preliminary Schedule Announced for 1988 APCA Annual Meeting

ABSTRACT

Stable heterogeneous catalysts for the oxidative removal of CO from air at ambient temperatures have been developed. An alumina support impregnated with PdCl₂, CuCl₂, and CuSO₄ is described. Optimal activity was obtained with Pd 0.020 mol/kg, Cu 0.50 mol/kg, CuCl₂ 20-30% of total Cu, a 2- to 24-hr soak, filtration of surplus raffinate, and a 2- to 4-hr firing in air at 200-350 °C. The catalysts are effective at 20-26 °C and relative humidities in the 15-90% range. They are reversibly deactivated by completely dry or water-saturated air streams. These catalysts have been tested at space velocities up to 30,000 hr^-1. In contact with <100 ppm CO, they are highly efficient, removing ~99% of the CO with contact times of ~120 msec (pseudo-first order k' > 25 sec^-1). At much higher CO concentrations, the maximum CO loading rate—limited by the Cu(I) reoxidation rate—is approximately 17 m mol CO per Limol Pd per hour.     

The Effects of Infiltration and Insulation on the Source Strengths and Indoor Air Pollution from Combustion Space Heating Appliances

Many energy conservation strategies for residences involve reducing house air exchange rates. Reducing the air exchange rate of a house can cause an increase in pollutant levels if there is an indoor pollution source and if the indoor pollutant source strength remains constant. However, if the indoor pollutant source strength can also be reduced, then it is possible to maintain or even improve indoor air quality. Increasing the insulation level of a house is a means of achieving energy conservation goals and, in addition, can reduce the need for space heating and thereby reduce the pollutant source strengths of combustion space heaters such as unvented kerosene space heaters, unvented gas space heaters, and wood stoves. In this paper, the indoor air quality trade-off between reduced infiltration and increased insulation in residences is investigated for combustion space heaters. Two similar residences were used for the experiment. One residence was used as a control and the other residence had infiltration and insulation levels modified. An unvented propane space heater was used as the source in this study. A model was developed to describe the dependence of both indoor air pollution levels and the appliance source strengths on house air exchange rates and house insulation levels. Model parameters were estimated by applying regression techniques to the data. Results show that indoor air pollution levels in houses with indoor combustion space heating pollution sources can be held constant (or lowered) by reducing the thermal conductance by an amount proportional to (or greater than) the reduction of the air exchange rate.     

Characterizing the Occurrence,Sources, and Variability of Radon in Pacific Northwest Homes

A compilation of data from earlier studies of 172 homes in the Pacific Northwest indicated that approximately 65 percent of the 46 homes tested in the Spokane River Valley/Rathdrum Prairie region of eastern Washington/northern Idaho had heating season indoor radon (²²²Rn) concentrations above the U. S. EPA guideline of 148 Bq m^?3 (4 pCi L^?1). A subset of 35 homes was selected for additional study. The primary source of indoor radon in the Spokane River Valley/Rathdrum Prairie was pressure-driven flow of soil gas containing moderate radon concentrations (geometric mean concentration of 16,000 Bq m^?3) from the highly permeable soils (geometric mean permeability of 5 × 10^?11 m²) surrounding the house substructures. Estimated soil gas entry rates ranged from 0.4 to 39 m³h^?1 and 1 percent to 21 percent of total building air infiltration. Radon from other sources, including domestic water supplies and building materials was negligible. In high radon homes, winter indoor levels averaged 13 times higher than summer concentrations, while in low radon homes winter levels averaged only 2.5 times higher. Short-term variations in indoor radon were observed to be dependent upon indoor-outdoor temperature differences, wind speed, and operation of forced-air furnace fans. Forced-air furnace operation, along with leaky return ducts and plenums, and openings between the substructure and upper floors enhanced mixing of radon-laden substructure air throughout the rest of the building.     

A Field Intercomparison and Fundamental Characterization of Various Dust Samplers with a Reference Sampler

The European Economic Community Council Directive 80/779/EEC¹ describes air quality limit values and guide values for sulfur dioxide and suspended particulates. However, article 10, paragraph 1 does not define well enough the reference method required, amongst others, for the gravimetric measurement of suspended particulates. It is explicity stated in article 10, paragraph 5 of the directive, that “the commission shall, in selected locations in the member states and in cooperation with the latter, carry out studies on the sampling…of suspended particulates. These studies shall be designed in particular to promote the harmonization of methods of sampling and analysis of these pollutants.” Therefore, in a joint research program the Umweltbundesamt (grant #104 02263), the commission of European Communities (grant #84-B-6642-11-017-11-N) and the U.S. EPA (grant #2-43211-3580) funded the development of a reference dust sampler by the Fraunhofer-lnstitute of Toxicology and Aerosol Research (FhITA, in Hannover, Federal Republic of Germany) in order: ? to study the particle size distribution of ambient air aerosol at a number of selected sites;

? to compare the results obtained with the reference dust sampler with those of particle samplers operated in Europe and the United States;

? to verify the applicability of wind tunnel results to sampling behaviour in the free atmosphere.