Organochlorine pesticides levels in Portuguese coastal areas.

Data on levels of persistent organochlorine pesticides (OCPs) that exhibit potentially harmful effects to the environment all over the Portuguese coastal sediments were scarce. Therefore, in 2007-2008 12 OCPs were surveyed in surface sediments from 11 coastal sites (estuarine or lagoonal) covering north, centre and south areas of Portugal. Analyzes were performed using a previously validated method, involving pre-extraction of OCPs from sediments assisted by microwave and headspace solid-phase microextraction followed by gas chromatography with electron capture detection for quantification and mass spectrometry for OCPs identification. Measurable levels (0.08-26ng g(-1)) of alpha-hexachlorocyclohexane (alpha -HCH), gamma-hexachlorocyclohexane (lindane), aldrin, dieldrin, endrin, 4,4'-DDT, 4,4'-DDD, 4,4'-DDE, heptachlor, heptachlor epoxide, endosulfan I and methoxychlor were observed in all cases. In few cases, the found levels denote the probability of occurrence of adverse biological effects.

Butyltin levels in several Portuguese coastal areas.

This work aimed to report present levels (2007-2008 sampling) of tri- (TBT), di- (DBT), and monobutyltin (MBT) in surface sediments from 11 Portuguese coastal sites and discuss the evolution of BTs contamination in the last two decades. All the samples revealed quantifiable values of TBT, DBT, and MBT with total butyltin concentrations between 1 and 565 ng/g (of Sn in dry sediment). Maximum level of TBT, 66 ng/g, was observed in Sado estuary, at Lisnave site, in the proximity of a big shipyard. MBT decreased site by site by the same order as DBT and TBT did, but its concentrations were much higher in many cases, denoting that TBT contamination was much higher in the past. A comparison with the available previous data confirmed a marked decrease of TBT contamination all over the last years, indicating that the main sources of TBT in Portuguese coastwise stopped effectively.

An expeditious method for the determination of organochlorine pesticides residues in estuarine sediments using microwave assisted pre-extraction and automated headspace solid-phase microextraction coupled to gas chromatography-mass spectrometry.

Determination of organochlorine pesticides (OCPs) in sediments implicates extraction of these compounds from the matrix, which is difficult owing to strong interaction among OCPs and different constituents of the sediments, particularly organic content. The method here described is a combination of microwave assisted extraction (MAE), headspace solid-phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS), acting in selected-ion storage mode, or GC-electron capture detector (ECD, for routine analysis). Methanol was used as extracting solvent and aliquots of the MAE extracts (after inclusion of a step for sulfur elimination when required) were used to prepare aqueous solutions for HS-SPME. A complete automation of the SPME procedure increases the sample throughput, including standard addition for calibration purpose. The procedure has the advantage of exclude additional clean-up steps and pre-concentration before SPME. Application to reference sediments of different characteristics revealed absence of significant interferences from the matrix for alpha-lindane, gamma-lindane, aldrin, dieldrin, endrin, 4,4'-DDT, 4,4'-DDD, 4,4'-DDE, heptachlor, heptachlor epoxide and good sensitivity. Detection limits ranged from 0.005 to 0.11 ng of OCP per gram of dried sediment using GC-MS and from 0.01 to 0.26 ngg(-1) using GC-ECD. The linear response ranges embraced 5-6 orders of magnitude (up to 1000 ngg(-1)) in GC-MS, being narrower for GC-ECD. The method was successfully applied to sandy and muddy sediments from Portuguese rivers estuaries, enabling quantification of seven OCPs. The method resulted effective, relatively simple and fast, being suitable for routine monitoring of residues of OCPs from sediments of different grain size and organic matter content, which influence concentration, mobility and availability of contaminants.