Monitoring of priority pesticides and other organic pollutants in river water from portugal by gas chromatography-mass spectrometry and liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.
ABSTRACT Gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) were optimized and applied for the trace-level determination of 42 priority pesticides and 33 priority organic pollutants from European Union Directive EC 76/464. First, off-line solid-phase extraction of 200 ml of river water using an OASIS solid-phase extraction cartridge, followed by GC-MS was used. Next, selected samples that were positive to GC-MS were analyzed by LC-APCI-MS in order to detect further polar byproducts or to improve the determination of previously detected polar analytes. The transformation products of triazine pesticides like deethylatrazine (DEA) and deisopropylatrazine (DIA) and compounds such as diuron and several chlorophenols were positively identified by LC-APCI-MS. The present methodology has also been used for searching for new analytes not included in the EC 76/464 list, like Irgarol, DEA and DIA. In addition it was applied to target pollutants in 43 river water samples from Portugal during a pilot survey from April to July 1999. Atrazine followed by simazine and 2,4,6-trichlorophenol were the most ubiquitous compounds detected in this area. The levels detected of the different compounds were in the range of: 0.01-2.73 microg/l, 0.05-0.74 microg/l, 0.02-1.65 microg/l, 0.02-5.43 microg/l, 0.01-0.40 microg/l, 0.01-0.26 microg/l, 0.02-0.61 microg/l, 0.01-3.90 microg/l, 0.01-1.24 microg/l, 0.02-2.3 microg/l, 0.01-0.13 microg/l and 0.01-0.5 microg/l for atrazine, simazine, terbuthylazine, alachlor, metolachlor, Irgarol, propanil; tributhylphosphate, diuron, 2,4,6-trichlorophenol, deisopropylatrazine and deethylatrazine, respectively.
Article: Pesticide levels in ground and surface waters of Primavera do Leste Region, Mato Grosso, Brazil.[show abstract] [hide abstract]
ABSTRACT: Residues of the herbicides simazine, metribuzin, metolachlor, trifluralin, atrazine, and two metabolites of atrazine, deisopropylatrazine (DIA) and deethylatrazine (DEA), are surveyed in the surface and groundwater of the Primavera do Leste region, Mato Grosso, Brazil during September and December 1998 and April 1999. Different water source sampling stations of groundwater (irrigation water well, drinking water well, and water hole) and surface water (dam and river) are set up based on agricultural land use. A solid-phase extraction procedure followed by gas chromatography-nitrogen-phosphorus detection is used for the determination of these compounds. All compounds are detected at least once in water samples. A temporal trend of pesticide contamination is observed, with the highest contamination frequency occurring in December during the main application season. Metribuzin shows the highest individual detection frequencies throughout the monitoring period, followed by metolachlor, simazine, and DEA. The maximum mean concentrations of pesticides in this study are in the range from 0.14 to 1.7 microg/L. We deduct that the contamination of water resources is predominantly caused by non-point pollution of pesticides used in intensive cash-crop cultures of the Cerrado area. Therefore, a continuous monitoring of pesticide concentrations in water resources of this tropical region is necessary to detect the longer term contamination trends and developing health risks.Journal of chromatographic science 09/2008; 46(7):585-90. · 0.88 Impact Factor
Article: Immunotoxicity in ascidians: antifouling compounds alternative to organotins - II. The case of Diuron and TCMS pyridine.[show abstract] [hide abstract]
ABSTRACT: Using short-term hemocyte cultures of the colonial ascidian Botryllus schlosseri exposed to various sublethal concentrations of Diuron (3-(3,4-diclorophenyl)-1,1-dimethylurea) and TCMS pyridine (2,3,5,6-tetrachloro-4-(metylsulphonyl)pyridine), we evaluated their immunotoxic effects through a series of cytochemical assays previously used for organotin compounds. At concentrations higher than 250 micro M and 10 micro M for Diuron and TCMS pyridine, respectively, both biocides exerted immunosuppressant effects on Botryllus hemocytes, causing i) deep changes in the cytoskeleton that irreversibly affect cell morphology and phagocytosis, ii) induction of DNA damage, iii) leakage of oxidative and hydrolytic enzymes due to membrane alteration. Unlike organotin compounds, Diuron and TCMS pyridine do not inhibit cytochrome-c-oxidase, and only TCMS pyridine triggers oxidative stress. When co-present, they exert an antagonistic interaction on cytoskeletal components.Journal of Environmental Science and Health Part B Pesticides Food Contaminants and Agricultural Wastes 12/2008; 43(8):644-54. · 1.10 Impact Factor
Article: Methodologies for the extraction of phenolic compounds from environmental samples: new approaches.[show abstract] [hide abstract]
ABSTRACT: Phenolic derivatives are among the most important contaminants present in the environment. These compounds are used in several industrial processes to manufacture chemicals such as pesticides, explosives, drugs and dyes. They also are used in the bleaching process of paper manufacturing. Apart from these sources, phenolic compounds have substantial applications in agriculture as herbicides, insecticides and fungicides. However, phenolic compounds are not only generated by human activity, but they are also formed naturally, e.g., during the decomposition of leaves or wood. As a result of these applications, they are found in soils and sediments and this often leads to wastewater and ground water contamination. Owing to their high toxicity and persistence in the environment, both, the US Environmental Protection Agency (EPA) and the European Union have included some of them in their lists of priority pollutants. Current standard methods of phenolic compounds analysis in water samples are based on liquid-liquid extraction (LLE) while Soxhlet extraction is the most used technique for isolating phenols from solid matrices. However, these techniques require extensive cleanup procedures that are time-intensive and involve expensive and hazardous organic solvents, which are undesirable for health and disposal reasons. In the last years, the use of news methodologies such as solid-phase extraction (SPE) and solid-phase microextraction (SPME) have increased for the extraction of phenolic compounds from liquid samples. In the case of solid samples, microwave assisted extraction (MAE) is demonstrated to be an efficient technique for the extraction of these compounds. In this work we review the developed methods in the extraction and determination of phenolic derivatives in different types of environmental matrices such as water, sediments and soils. Moreover, we present the new approach in the use of micellar media coupled with SPME process for the extraction of phenolic compounds. The advantages of micellar media over conventional extractants are reduction of organic solvent, low cost, easy handling and shorter time procedures.Molecules 02/2009; 14(1):298-320. · 2.39 Impact Factor