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.     

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.     

Deriving environmental quality standards in European surface waters: when are there too few data?

Recent technical guidance has been published by the European Commission that outlines methodologies for the derivation of Environmental Quality Standards (EQS) in European surface waters under the Water Framework Directive (WFD). The guidance allows the derivation of a long-term EQS from a small dataset. Specifically an EQS can be derived from just three acute data points, although the safety factors built into such an EQS are large (e.g. up to a factor of 1,000). Large safety factors make such EQS uncertain, and often difficult to achieve in practice. We examine dataset requirements for the derivation of EQS and specifically the minimum number of tests needed for setting EQS for long-term chemical exposures that result in reduced relative uncertainty, as assessed simply through the reduction in standard deviation of the means of the values derived. Using ecotoxicity datasets for four example chemicals, for which EQS have been derived in many jurisdictions, we show that variation in the EQS is greatest when using the minimum dataset allowable under the WFD guidance, but decreases rapidly when seven or more datapoints are available. Increasing the minimum number of ecotoxicity data in deriving an EQS results in a greater understanding of ecotoxicological effects. With this knowledge, the mitigating effects of water chemistry can be accounted for in deriving an EQS, even with relatively limited datasets. The new guidance suggests “simplistic” approaches to account for chemical availability, but does not detail how this might be undertaken. We provide examples of ways by which water chemistry effects can be included in deriving implementable EQS for metals with relatively few reliable and relevant data.     

Carbon accumulation through ecosystem recovery

A market has emerged for carbon sequestered through reforestation. The opportunity to restore ecosystems through this market rather than establish plantations is demonstrated by an Australian case study. In the state of Queensland there are vast areas that have been cleared relatively recently and could be restored to ecosystems with high resilience and important biodiversity values with appropriate management. In order to foster opportunities for carbon accumulation through ecosystem recovery spatially explicit information on sequestration rates, management recommendations, and clear definitions of ancillary biodiversity benefits need to be defined.     

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.

     

Improved performance of a biomaterial-based cation exchanger for the adsorption of uranium(VI) from water and nuclear industry wastewater

The amine-modified polyhydroxyethylmethacrylate (poly(HEMA))-grafted biomaterial (tamarind fruit shell, TFS) carrying carboxyl functional groups at the chain end (PGTFS-COOH) was prepared and used as an adsorbent for the removal of uranium(VI) from water and nuclear industry wastewater. FTIR spectral analysis revealed that U(VI) ions and PGTFS-COOH formed a chelate complex. The adsorption process was relatively fast, requiring only 120 min to attain equilibrium. The adsorption kinetic data were best described by the pseudo-second-order equation. The equilibrium adsorption data were correlated with the Sips isotherm model. The maximum U(VI) ions uptake with PGTFS-COOH was estimated to be 100.79 mg/g. The complete removal of 10 mg/L U(VI) from simulated nuclear industry wastewater was achieved by 3.5 g/L PGTFS-COOH. The reusability of the adsorbent was demonstrated over 4 cycles using NaCl (1.0 M) + HCl (0.5 M) solution mixture to de-extract the U(VI). The results show that the PGTFS-COOH tested is very promising for the recovery of U(VI) from water and wastewater.