Environmental fate of pesticides used in Australian viticulture IV. Aqueous stability of dithianon

Dithianon formulations are unstable in slightly basic aqueous solutions (pH 9, 20°C, t _½ = 5.6 h) but relatively stable in neutral or acidic solution (pH 4,20°C, t _½ = 6443 h). To ensure the efficacy of this fungicide it is important to prepare the spray mix fresh with neutral or slightly acidic water. Dithianon is unstable towards natural sunlight in the solid and aqueous phase, with half‐lives of approximately 68 and 42 days, respectively. Thermal hydrolysis does not seem to be the preferred degradation pathway when aqueous solutions are heated by the South Australian summer sun. The major aqueous phase photodegradation product has been identified as 2,3‐dihydro‐1,4‐dithiaanthraquinone. These results strongly suggest that should dithianon be accidentally released into basic Australian waters then it is likely to be rapidly chemically hydrolysed and pose little long term environmental threat. However, dithianon is only slowly chemically and photo‐lytically hydrolysed in neutral and acidic waters, and in this case accidentally release may pose a significant short term environmental threat.     

Environmental fate of pesticides used in Australian viticulture: Behaviour of dithianon and vinclozolin in the soils of the South Australian Riverland

The red calcareous earth soils of the South Australian Riverland produce more than one-third of the grapes used in Australian winemaking. As part of on-going investigations into pesticide transport in Australian vineyard soils, the movement of the fungicides dithianon and vinclozolin through such strongly alkaline soils was investigated. Small, undisturbed soil cores were extracted from the inter-row topsoil of a vineyard adjacent to the River Murray, approximately 10 km S.W. of Overland Corner, South Australia. The vines were grown in a deep (1 – 4 m) reddish brown, strongly alkaline, sandy loam with a low organic carbon content (1 – 2 %). Surface fluxes of pesticide were applied at the maximum recommended application rates to the surface of the cores, which were then irrigated, and pesticide residues in the leachate determined by HPLC. No leaching of either dithianon or vinclozolin occurred. Dithianon was immobilised in the top 2 cm of the soil. Dithianon concentrations were low ( 0 – 37 % applied dose) suggesting that rapid degradation of this compound occurs in these soils (63 – 100 % degradation in 10 days). Extremely low concentrations of vinclozolin were found throughout the soil core profiles (0.05 – 1.4 % applied dose) suggesting that this fungicide was somewhat mobile, but also that it too was unstable in such alkaline soils (> 98 % degradation in 10 days). These results suggest that the irrigated vineyard soils of this region are unlikely to be prone to leaching of dithianon or vinclozolin, and therefore that groundwater supplies in this area are unlikely to be at any significant risk of contamination through viticultural use of these compounds.     

Application of an inclusion complex for determination of dithianon residues in water and fruits

A 3,3′-benzidine/β-cyclodextrin fluorescence derivative (BCDFD) was prepared and characterized by means of elemental analysis and ¹H NMR. An inclusion complex was formed between BCDFD and the pesticide dithianon based on the internal cavity of β-cyclodextrin (β-CD), and the binding constant (K_S ) of the inclusion complex was investigated. The inclusion complex could be applied for the determination of dithianon residues. Based on this, a sensitive method for the determination of dithianon was established. The linear dynamic range was from 0.63 to 12.5?mg?L^?1 with a correlation coefficient of 0.9927. The limit of detection for an aqueous solution of standard and the relative standard deviation (RSD) were 10.6?µg?L^?1 and 0.76%, respectively. The proposed method has been successfully applied for the determination of dithianon residues in water and fruit samples with satisfactory results, and recoveries in the range of 96.0–108% were obtained. The method is rapid, direct, economical, and sensitive for dithianon analysis.     

Environmental fate of pesticides used in Australian viticulture III. Fate of dithianon from vine to wine

Pinot noir, bastardo, rkaziteli and semillon grapes on vines grown in the Barossa Valley of South Australia were treated with a commercial dithianon formulation. The grapes were harvested by hand eight days later, and made into wine. Grab samples of berries, grape juice and the young wine were analysed for fungicide residues. No dithianon was detected in control grape samples, grape juices or wines. Significant dithianon levels were detected on the skins of treated grape samples. Dithianon is stable on the surface of grapes under the ambient conditions prevalent under the grape canopy for at least two weeks. No dithianon was detected in grape juice, on grape skins after berry crushing, in the lees, or in the young wine. Dithianon is unstable in grape juice and wine. Dithianon half‐life (initial concentration = 1 μg/mL) in semillon grape juice = 2.8 h, semillon wine = 0.58 h, pinot noir grape juice = 4.6 h, and pinot‐noir wine = 0.29 h. Treatment with fining agents or heat does not significantly reduce the rate of degradation. These results suggest that spraying table grapes with dithianon two weeks before harvest would result in exposure to essentially the full dose of active ingredient sprayed, and increase the risk to human health through ingestion of this compound. However, any threat to human health from ingestion through grape juice or wine is limited since any contact with grape juice or wine leads to rapid decomposition of dithianon by some as yet undetermined process.