Problemas en el análisis de metilsiloxanos volátiles (VMS): origen y soluciones

Volatile methylsiloxanes (VMS) are pollutants widely distributed in the environment due to its extensive uses and high volatility. The analysis of these compounds is commounly performed by gas chromatography - mass spectrometry (GC-MS), and it is dificult due to the presence of background contamination and volatile losses. Different preconcentration techniques such as purge and trap (P&T), headspace (HS) and headspace - solid phase microextraccion (HS-SPME) have been applied for the analysis of VMS in environmental samples. Alternatively, solvent extraction combined with large volume injection techniques has been an effective method for the analysis of complex matrices (eg. wastewater, sludges). In this review, the efficiency of the different methods reported for the analysis of VMS is discussed, and different solutions are proposed to minimize background contamination and volatilization

Nuevas estrategias para la determinación de polisiloxanos en muestras ambientales

[spa] Los metilsiloxanos volátiles (VMS) constituyen un nuevo grupo de contaminantes cuya presencia en el medio ambiente ha suscitado en los últimos años una especial atención debido a que presentan una elevada persistencia, capacidad de bioacumulacion y provocan efectos tóxicos y potencialmente cancerígenos en los organismos vivos. Hasta el momento, los datos disponibles sobre su presencia y distribución en el medio ambiente son muy limitados y, por tanto, existe un gran interés por conocer el impacto real que provocan estos contaminantes. Además, el análisis de estos compuestos en muestras ambientales conlleva serias dificultades debido a su elevada volatilidad y a la contribución como contaminación de fondo a las muestras. En base a esta problemática, el objetivo de esta tesis es el desarrollo de nuevos métodos de análisis para la determinación de VMS mediante la cromatografía de gases acoplada a espectrometría de masas (GC-MS), y estudiar su presencia y distribución en muestras ambientales de diferente naturaleza. Debido a que los VMS son compuestos de elevada volatilidad, en esta tesis se han desarrollado métodos de análisis empleando la técnica HS-SPME para el análisis de VMS en aguas fluviales y mejillones. También se utilizaron discos de extracción en fase sólida (SPE disk) de C18 de pequeño formato (5,5mg/1ml) para el anàlisis de la fase disuelta de aguas residuales. Para el análisis de la fase particulada del agua residual, además de suelos y lodos se utilizó la extracción con n-hexano y purificación del extracto con cartucho de SPE de sílice (100mg/1ml). En esta tesis también se ha abordado el análisis de VMS en aire mediante el uso de cartuchos de isolute ENVI+ para la retención de los analitos. Se aplicó la inyección de grandes volúmenes con la técnica Concurrent solvent recondensation-large volume injection (CSR-LVI), para incrementar sensibilidad de la determinación en todos los métodos establecidos. Los métodos desarrollados fueron aplicados al análisis de diferentes tipos de muestras, como suelos urbanos, lodos de depuradoras, aguas residuales sin tratar y tratadas, aire de exterior e interior y mejillones. En todas las muestras, las concentraciones encontradas de VMS mostraron un elevado predominio de los VMS cíclicos respecto a los lineales, siendo el decametilciclopentasiloxano (D5) el compuesto mayoritario. En general, las matrices más contaminadas con VMS fueron las aguas residuales y lodos de depuradoras, mientras que los niveles más bajos se encontraron en agua fluvial y suelos urbanos. El estudio de VMS en mejillones como bioindicadores de contaminación ha permitido detectar la presencia de estos compuestos en aguas de la costa catalana y determinar las zonas que presentan un mayor grado de contaminación.[eng] Volatile methylsiloxanes (VMS) constitutes a new group of pollutants that has attracted special attention in recent years, because of their high persistence, bioaccumulation capacity, toxicity and potentially carcinogenic effects in living organisms. So far, data available about their presence and distribution in the environment are very scarce and therefore, studying the real impact caused by these contaminants is very interesting. On the other hand, the analysis of these compounds in environmental samples is very difficult due to their high volatility and their presence as background contaminants in the samples. Based on these facts, the aim of this work was the development of new analytical methods for the determination of VMS by gas chromatography coupled to mass spectrometry (GC-MS), and studying their presence and distribution in different types of environmental samples. Due to their high volatility, the analysis of VMS in river waters and mussels was carried out applying the HS-SPME technique. For the analysis of the dissolved phase of wastewaters, C18 solid phase extraction disks cartridges in small format (5.5 mg / 1 ml) were used. For analysis of the particulate phase of the wastewaters, soils and sludge samples, extraction with n-hexane followed by purification of the extract with silica SPE cartridge (100 mg / 1 ml) was used. The analysis of VMS in ambient air was carried out using isolute ENVI + cartridges for the sampling. Concurrent solvent recondensation-large volume injection (CSR-LVI) technique was used to increase sensitivity of the determination. The developed methods were applied to the analysis of different types of samples, such as urban soil, sewage sludge, wastewaters, indoor and outdoor air and mussels. In all the samples, a high prevalence of cyclic VMS were found with decamethylcyclopentasiloxane (D5) as the major component. In general, matrices with the higher pollution levels were wastewaters and sewage sludges, while the lowest levels were found in river waters and urban soils. The use of mussels as bioindicators of pollution allowed the detection of methylsiloxanes in the Catalan coast seawater identifying the areas with higher pollution

Anthropogenic hydrocarbons in sediments of the northeastern Havana seaboard

The presence of petrogenic hydrocarbons was evaluated in surface sediments from the northeastern Havana littoral (Cuba). Different geochemical biomarkers were used to differentiate between biogenic and anthropogenic hydrocarbons. Sediment samples were Soxhlet extracted and analyzed by gas chromatography with flame ionization and mass spectrometer detectors. Total concentrations of aliphatic hydrocarbons ranged from 5.5 ± 0.3 to 225.7 ± 12.6 µg g–1. The presence of an unresolved complex mixture, and the detection of hopanes and of the isoprenoid compounds pristane and phytane revealed the occurrence of petroleum-derived hydrocarbons in the sediment samples.

Validation of an analytical methodology for the quantitative analysis of petroleum hydrocarbons in marine sediment samples

This work describes a validation of an analytical procedure for the analysis of petroleum hydrocarbons in marine sediment samples. The proposed protocol is able to measure n-alkanes and polycyclic aromatic hydrocarbons (PAH) in samples at concentrations as low as 30 ng/g, with a precision better than 15% for most of analytes. The extraction efficiency of fortified sediments varied from 65.1 to 105.6% and 59.7 to 97.8%, for n-alkanes and PAH in the ranges: C16 - C32 and fluoranthene - benzo(a)pyrene, respectively. The analytical protocol was applied to determine petroleum hydrocarbons in sediments collected from a marine coastal zone