Seasonal distributions of fungicides in soils and sediments of a small river basin partially devoted to vineyards.

The acid soils of Ourense province riverland (Galicia, NW Spain) produce about 50,000 tons of grapes for winemaking. As part of ongoing investigations into fungicide transport in Ourense vineyard soils, the occurrence of several fungicides in such soils was investigated. Soil samples were collected from the inter-row topsoil of a vineyard adjacent to the River Alongos, approximately 15 km SW of the main city of Ourense. The vines were grown in sandy loam with moderate organic carbon (OC) content (1-2%). Fungicide residues were measured in vineyard soils and river sediments by solid-liquid extraction followed by gas chromatography with mass spectrometric detection (GC-MSD). Procymidone and cyprodinil occurred at higher levels in river sediments than in the case of fludioxonil, metalaxyl and penconazole. The highest concentrations of procymidone in sediments were still low (29-57 microg/kg or ppb) suggesting that no accumulation of these compounds occur. All of them were found at higher concentrations in soil; maxima concentrations were about 1000 microg/kg for procymidone and metalaxyl, and about 400 microg/kg for cyprodinil, fludioxonil and penconazole. Folpet was never detected (detection limit lower than 2 microg/kg) in soil and sediments, suggesting that this fungicide was unstable in such samples. The frequency of fungicide detections in soils can be related to their applications in vineyards and the effect of washing off through vineyard canopy by rainfalls. The results found suggest that the vineyard soils of this region are unlikely to be prone to transport of fungicides, and therefore water supplies in this area are unlikely to be at any significant risk of contamination through viticultural use of these compounds.

Evolution of the concentrations of polycyclic aromatic hydrocarbons in burnt woodland soils.

Little is known of the fate of polycyclic aromatic hydrocarbons (PAHs) in soils under burnt woodland. It is not clear what the behavior of the overlying wood ash layer will be along months. In this study, the levels of eight representative PAHs in the 1-5 cm layer of a periurban woodland soil that had undergone wildfire were compared with those measured in nearby and distant unburnt periurban woodland soils and in a distant unburnt rural woodland soil, and the levels at the burnt site were monitored during some 10 months. The analytical method optimized for the purpose afforded recoveries of 74-111% (depending on PAH) and repeatabilities (RSDs) better than 9%, with limits of detection ranging from 1 to 7 microg/kg. PAH levels in the 1-5 cm layer of the burnt periurban soil were very similar to those of distant unburnt periurban soil (188 vs 173 microg/kg), about seven times the 26 microg/kg measured in unburnt rural soil, which furthermore contained no detectable quantities of the highest molecular weight PAHs typical of traffic and other urban sources, as the periurban soils did. At the burnt site, PAH levels fell along the months (the total PAH level from 188 to 119 microg/kg), apparently as the result of rainfall and the prevention of further input from the atmosphere by the overlying layer of wood ash, which had a very high PAH adsorption capacity (1169 microg/kg) and did not itself appear to act as a source of PAHs. PAH transport may have been assisted by increased mobilization of PAHs associated with dissolvable organic matter due to an increase in soil pH due to alkaline ash components.

Occurrence of organochlorine pesticides in stream sediments from an industrial area.

Contaminated stream sediments are a serious problem because contaminant residues will be persistent for a long time. Organochlorine pesticides (OCPs) were screened in stream sediments collected along stream flows close to an industrial area in northwestern Spain. Analyses were performed by extraction with organic solvents followed by gas chromatography-mass spectrometry detection. OCPs such as hexachlorobenzene, hexachlorocyclohexane (alpha and beta isomers) and DDT were detected at levels ranging between 29 and 392 microg/kg indicating there is a moderate to severe pollution in the area even though they were banned a few decades ago.

Procedure to measure the level of polycyclic aromatic hydrocarbons in wood ashes used as fertilizer in agroforestry soils and their transfer from ashes to water.

Before wood ash can be safely used as a fertilizer in soils, possible negative effects such as input of organic contaminants or remobilization of contaminants already stored in the soil must be investigated. The objective of this study was to optimize and characterize extraction methods to isolate and quantitatively measure polycyclic aromatic hydrocarbons (PAHs) concentrations in wood ash that can be used as amendment of soils. It will be then possible to examine the effects of wood ash application on PAHs concentrations in the washing waters with the aim of evaluating their distribution by storage in the different compartments and what influences their stability and persistence. Simple, rapid and inexpensive methods have been set up for the determination of seven polycyclic aromatic hydrocarbons (PAHs) in wood ashes and ash aqueous extracts without interferences from other chemical contaminants using organic solvent extraction and/or SPE techniques and analyzed by an optimized RP-HPLC-FLD method. The feasibility of extraction for the determination of PAHs in wood ashes has been evaluated because PAHs are strongly sorbed to such a matrix, which explains why the PAHs content in ash was seldom studied. The method resulted to be of recoveries ranging from 81 to 97% for the different PAHs, with repeatabilities (RSDs%) better than 6%. Detection levels were from 0.2 to 2.2 microg/kg, while quantification limits were from 0.7 to 5.6 microg/kg, low enough to evaluate the presence of PAHs in wood ashes.