Evaluation of the performance of the short-listed candidate markers regarding the technical requirements: Call for expression of interest to present products suitable for use as a marker in gas oils and kerosene

The European Commission adopted the Euromarker (SY124) in 2001 as a common pan-European fiscal marker to label gas oil and kerosene. In parallel, several other marking systems based on other dyes and markers were already in use in different member states. Generally the use of a marker makes it possible to sell fuel with a lower tax for use in dedicated sectors like agriculture, marine use and for domestic heating. In contrast, non-marked fuels are normally fully taxed and intended for road transport. Unfortunately SY124 is easy to remove or destroy which has made wide-spread fraud possible. This has resulted in substantial losses of tax revenue and a number of member states have repeatedly notified the European Commission of this problem. Some member states currently invest considerable amounts of resources and effort in tracking illegal use of laundered fuel by performing >10,000 measurements per year of SY124 in gasoil and diesel. Other member states have recently adopted a new national marker to prevent this kind of fraud. To improve the situation on a European level DG TAXUD published an open call in order to find a new marker that could potentially replace SY124 as Euromarker. To support DG TAXUDs policies to find a better fiscal marker, JRC has performed different kinds of tests resulting in more than 1200 samples for checking resilience of four candidate markers alongside with SY124. Generally the tests involved laundering over different adsorbents, chemical break-down and different physical treatments. All new candidate markers are colourless but road-side detection of the candidate markers is possible and based on dedicated instrumentation. Based on these experiments one candidate marker outperforms the others and is resilient to most treatments. This candidate marker could potentially be used to replace SY124.JRC.F.6-Reference Material

CERTIFICATION REPORT: The certification of the mass fraction of Solvent Yellow 124 in gas oil: ERM®-EF318k

This report describes the production of ERM®-EF318k, which is a matrix material certified for the mass fraction of Solvent Yellow 124, SY124. It is a remake of ERM-EF318, which is out of stock since 2016. This material was produced following ISO Guide 34:2009 and is certified in accordance with ISO Guide 35:2006. The starting materials were commercially available B0 gas oil (B0: without biodiesel) and SY124 produced as a CRM (ERM-AC316a). The material was prepared gravimetrically using calibrated balances and the mass fraction was confirmed by independent measurements. The solution of SY124 in gas oil was ampouled under argon atmosphere and stored at 18 °C in the dark. Between-unit homogeneity was quantified and stability during dispatch and storage were assessed in accordance with ISO Guide 35:2006 [2]. The minimum sample intake was established based on the data available in the certification report of ERM-EF318. The certified value was obtained from the gravimetric preparations, taking into account the purity of the base materials. The certified value was confirmed by HPLC-UV, i.e. Community Reference Method to analyse SY124, as an independent verification method (measurements were within the scope of accreditation to ISO/IEC 17025:2005). The uncertainty of the certified value was calculated in accordance with the Guide to the Expression of Uncertainty in Measurement (GUM) [6] and includes uncertainties related to possible inhomogeneity, instability and characterisation. The material is intended for the quality control / assessment of method performance. As with any reference material, it can be used for establishing control charts or validation studies. The CRM is available in amber glass ampoules containing at least 4.2 mL of gas oil which were sealed under an atmosphere of argon. The minimum amount of sample to be used is 20 µL.JRC.F.6-Reference Material

Hydrocarbons in the open ocean waters near the Galician Bank after the deep sea spill from the Prestige wrecks

Tesis del Departament de Ciencia i Tecnologia Ambientales de la Universitat Atònoma de Barcelona (UAB).-- Fecha de defensa[ESP] Hoy en día existe una escasez de estudios sobre la distribución de los hidrocarburos en mar abierto, aunque el aumento de la explotación de yacimientos de petróleo y la intensificación del tráfico marítimo más allá de la plataforma continental haya aumentado. Asimismo, se han identificado nuevas fuentes de contaminación. En los últimos años se ha puesto en evidencia el alto número de barcos hundidos en los fondos marinos que podrían potencialmente generar futuros vertidos de petróleo.En esta tesis, se investiga el accidente del petrolero Prestige cerca de Galicia en el 2002 como caso de estudio de un vertido marino en profundidad en mar abierto, ya que aproximadamente unas 43.000 toneladas de fuel oil pesado que llevaba a bordo fueron vertidas una vez el barco de rompió en dos y se hundió. Además, la zona del hundimiento del Prestige es un área hidrodinámicamente compleja. La columna de agua esta formada por cinco masas de aguas principales, de diferente origen y con características físico-químicas diferentes, que pueden contribuir activamente extender el fuel liberado por el Prestige en las aguas cerca del Banco de Galicia.En este contexto, el principal objetivo de la presente tesis ha sido determinar la importancia de los pecios del Prestige como fuente de contaminación en las aguas cerca del Banco de Galicia varios años después del accidente e investigar el papel de las masas de agua en el transporte y distribución de los hidrocarburos en la zona del hundimiento. Estos objetivos se han alcanzado mediante la combinación de estudios de laboratorio y trabajo de campo. Por un lado, se realizaron diferentes experimentos bajo condiciones estables de temperatura y salinidad que dieron información sobre la disolución potencial del fuel del Prestige en agua marina. Además, dos campañas oceanográficas se llevaros a cabo en marzo y octubre del 2006 cerca de los pecios y las zonas adyacentes, con el objetivo de recoger agua marina. Se determinaron hidrocarburos en la materia sólida en suspensión y la fase disuelta del agua en la columna de agua de las tres estaciones. Una se encontraba encima de los pecios del Prestige mientras que las otras dos se localizaron a 73 millas náuticas, una al norte y la otra al sur de este punto.En marzo del 2006, en la zona del hundimiento y en las otras dos estaciones, las concentraciones de hidrocarburos de origen petrogénico estaban dentro el rango los niveles descritos en la literatura para áreas similares, mientras que los niveles en octubre del mismo año era superiores. Las concentraciones de hidrocarburos poliaromáticos encontrados en la fase disuelta eran, tanto en marzo como en octubre, mucho mayores que los niveles de referencia establecidos para la zona. La huella química de los hidrocarburos en octubre del 2006 indicó que los pecios del Prestige habían estado liberando fuel oil durante varios años después del accidente. Sin embargo, a pesar de la amplia presencia de hidrocarburos provenientes del petróleo en la columna de agua de las tres estaciones, no se puede afirmar que el Prestige constituía la fuente más importante de contaminación en le área, ya que los hidrocarburos parecían provenir de múltiples orígenes. De hecho, varias masas de agua presentan contenidos distintivos de hidrocarburos en la fase disuelta y material particulado.El estudio realizado se puede entender como un ejemplo del potencial de un pecio hundido en el Noratlántico profundo como fuente de contaminación. Aunque cada pecio representa un caso único, el conocimiento obtenido sobre la distribución espacial y temporal de los hidrocarburos después del accidente del Prestige se puede utilizar en futuros vertidos.[ENG] There is an apparent shortage of studies on the distribution and fate of oil hydrocarbons in open ocean waters. Nevertheless, given the increasing exploitation of oilfields in the high seas, and the intensification of maritime traffic, in the last decades, oil pollution of the marine environment beyond the continental platforms is increasing. In addition, new sources of pollution are being recognized. Thus, in recent years it has been noted that the high number of sunken vessels scattered in the oceans sea floor are potentially a present and future source of oil spills.In this thesis, the accident of the Prestige tanker in 2002 off the Galician coast is investigated as a case study of a deep sea spill in open ocean waters, since around 43,000 tonnes of heavy fuel oil were spilled after the vessel broke in two and sank. In addition, the area near the Galician Bank, where the Prestige wrecks are located, is hydrodynamically complex. The water column is comprised by five main water masses from different origins and physico-chemical properties, which may contribute to actively spread the oil released from the Prestige in different and distinct ways.In this context, the main aim of this study has been to determine the importance of the Prestige shipwrecks as a source of oil pollution in the waters near the Galician Bank several years after the accident took place and to investigate the role of the water masses in the sinking area in the transport and distribution of hydrocarbons. These objectives have been tackled by a combination of laboratory and field studies. First of all, several sets of experiments were carried out under controlled temperature and salinity conditions which provided information about the potential dissolution of the Prestige fuel oil in seawater. In addition, two oceanographic cruises were undertaken in March and October 2006, near the wrecks location and surrounding areas, to collect seawater samples. Hydrocarbons were determined in the suspended particulate matter (SPM) and dissolved phase (DP) in the water column of three stations. One was located above the Prestige wrecks, and the other two 73 nautical miles north and south of the Prestige incident area.Hydrocarbons concentrations from petrogenic sources in the SPM above the wreck and surrounding areas in March 2006 were within the range of abundances previously reported for similar areas, but much higher in October 2006. The concentrations of polycyclic aromatic hydrocarbons found in the DP were, both in March and October 2006, well above any expected background levels. The chemical fingerprint of the hydrocarbons indicated that in October 2006 the oil at the Prestige station originated from the wrecks. This, together with the unusually high relative concentration of hydrocarbons in the DP at the Prestige station in March 2006, indicates that the Prestige wrecks had been releasing oil for several years after the accident. However, despite the widespread occurrence of oil hydrocarbons in the three stations and throughout their water columns, it could not be concluded that the Prestige was the main source of pollution in the area near the Galician bank, which most likely has multiple origins. In fact, different water masses contain distinct contents of hydrocarbons in the SPM and the DP, which in some instances may have remote sources.The study conducted can be viewed as an example of the potential of a sunken wreck in the deep North Atlantic as a source of pollution. Although each potentially polluting shipwreck represents a singular case, knowledge obtained about the temporal and spatial distribution of hydrocarbons after the accident of the Prestige could be applied to deal with other deep spills in the future.Peer reviewe

Phase distribution of hydrocarbons in the water column after a pelagic deep ocean oil spill

Spills from wrecks are a potential major source of pollution in the deep ocean. However, not much is known about the fate of a spill at several kilometers depth, beyond the oceans continental shelves. Here, we report the phase distribution of hydrocarbons released from the wrecks of the Prestige tanker, several years after it sank in November 2002 to depths between 3500 and 3800 m. The released oil reached the surface waters above the wrecks without any signs of weathering and leaving an homogenous signature throughout the water column. At depths of several kilometers below the sea surface, the occurrence and spread of the deep sea oil spill could be evaluated better by quantifying and characterizing the dissolved hydrocarbon signature, rather than just the investigation of hydrocarbons in the suspended particulate matter.Authors acknowledge the Spanish government for funding (VEM2003-20583) and the Generalitat of Catalonia for a studentship to S.E.Z. Erin McClymont, Ester Garcia, Raquel Hernandez, Alfredo Martinez, Carolina Olid, Sara Orgué, Barend van Droogue and the crew of the Cornide de Saavedra are thanked for their assistance during the expeditions, Juan J. Gonzalez and Demetrio de Armas for providing logistical support during the October 2009 cruise, and Manh Hieu for laboratory assistance. The IAEA is grateful for the support provided to its Marine Environment Laboratories by the Government of the Principality of Monaco.Peer reviewe

Hydrocarbons in the open ocean waters near the Galician Bank after the deep sea spill from the Prestige wrecks

Descripció del recurs: el 16 de juny de 2010Hoy en día existe una escasez de estudios sobre la distribución de los hidrocarburos en mar abierto, aunque el aumento de la explotación de yacimientos de petróleo y la intensificación del tráfico marítimo más allá de la plataforma continental haya aumentado. Asimismo, se han identificado nuevas fuentes de contaminación. En los últimos años se ha puesto en evidencia el alto número de barcos hundidos en los fondos marinos que podrían potencialmente generar futuros vertidos de petróleo. En esta tesis, se investiga el accidente del petrolero Prestige cerca de Galicia en el 2002 como caso de estudio de un vertido marino en profundidad en mar abierto, ya que aproximadamente unas 43.000 toneladas de fuel oil pesado que llevaba a bordo fueron vertidas una vez el barco de rompió en dos y se hundió. Además, la zona del hundimiento del Prestige es un área hidrodinámicamente compleja. La columna de agua esta formada por cinco masas de aguas principales, de diferente origen y con características físico-químicas diferentes, que pueden contribuir activamente extender el fuel liberado por el Prestige en las aguas cerca del Banco de Galicia. En este contexto, el principal objetivo de la presente tesis ha sido determinar la importancia de los pecios del Prestige como fuente de contaminación en las aguas cerca del Banco de Galicia varios años después del accidente e investigar el papel de las masas de agua en el transporte y distribución de los hidrocarburos en la zona del hundimiento. Estos objetivos se han alcanzado mediante la combinación de estudios de laboratorio y trabajo de campo. Por un lado, se realizaron diferentes experimentos bajo condiciones estables de temperatura y salinidad que dieron información sobre la disolución potencial del fuel del Prestige en agua marina. Además, dos campañas oceanográficas se llevaros a cabo en marzo y octubre del 2006 cerca de los pecios y las zonas adyacentes, con el objetivo de recoger agua marina. Se determinaron hidrocarburos en la materia sólida en suspensión y la fase disuelta del agua en la columna de agua de las tres estaciones. Una se encontraba encima de los pecios del Prestige mientras que las otras dos se localizaron a 73 millas náuticas, una al norte y la otra al sur de este punto. En marzo del 2006, en la zona del hundimiento y en las otras dos estaciones, las concentraciones de hidrocarburos de origen petrogénico estaban dentro el rango los niveles descritos en la literatura para áreas similares, mientras que los niveles en octubre del mismo año era superiores. Las concentraciones de hidrocarburos poliaromáticos encontrados en la fase disuelta eran, tanto en marzo como en octubre, mucho mayores que los niveles de referencia establecidos para la zona. La huella química de los hidrocarburos en octubre del 2006 indicó que los pecios del Prestige habían estado liberando fuel oil durante varios años después del accidente. Sin embargo, a pesar de la amplia presencia de hidrocarburos provenientes del petróleo en la columna de agua de las tres estaciones, no se puede afirmar que el Prestige constituía la fuente más importante de contaminación en le área, ya que los hidrocarburos parecían provenir de múltiples orígenes. De hecho, varias masas de agua presentan contenidos distintivos de hidrocarburos en la fase disuelta y material particulado. El estudio realizado se puede entender como un ejemplo del potencial de un pecio hundido en el Noratlántico profundo como fuente de contaminación. Aunque cada pecio representa un caso único, el conocimiento obtenido sobre la distribución espacial y temporal de los hidrocarburos después del accidente del Prestige se puede utilizar en futuros vertidos.There is an apparent shortage of studies on the distribution and fate of oil hydrocarbons in open ocean waters. Nevertheless, given the increasing exploitation of oilfields in the high seas, and the intensification of maritime traffic, in the last decades, oil pollution of the marine environment beyond the continental platforms is increasing. In addition, new sources of pollution are being recognized. Thus, in recent years it has been noted that the high number of sunken vessels scattered in the oceans sea floor are potentially a present and future source of oil spills. In this thesis, the accident of the Prestige tanker in 2002 off the Galician coast is investigated as a case study of a deep sea spill in open ocean waters, since around 43,000 tonnes of heavy fuel oil were spilled after the vessel broke in two and sank. In addition, the area near the Galician Bank, where the Prestige wrecks are located, is hydrodynamically complex. The water column is comprised by five main water masses from different origins and physico-chemical properties, which may contribute to actively spread the oil released from the Prestige in different and distinct ways. In this context, the main aim of this study has been to determine the importance of the Prestige shipwrecks as a source of oil pollution in the waters near the Galician Bank several years after the accident took place and to investigate the role of the water masses in the sinking area in the transport and distribution of hydrocarbons. These objectives have been tackled by a combination of laboratory and field studies. First of all, several sets of experiments were carried out under controlled temperature and salinity conditions which provided information about the potential dissolution of the Prestige fuel oil in seawater. In addition, two oceanographic cruises were undertaken in March and October 2006, near the wrecks location and surrounding areas, to collect seawater samples. Hydrocarbons were determined in the suspended particulate matter (SPM) and dissolved phase (DP) in the water column of three stations. One was located above the Prestige wrecks, and the other two 73 nautical miles north and south of the Prestige incident area. Hydrocarbons concentrations from petrogenic sources in the SPM above the wreck and surrounding areas in March 2006 were within the range of abundances previously reported for similar areas, but much higher in October 2006. The concentrations of polycyclic aromatic hydrocarbons found in the DP were, both in March and October 2006, well above any expected background levels. The chemical fingerprint of the hydrocarbons indicated that in October 2006 the oil at the Prestige station originated from the wrecks. This, together with the unusually high relative concentration of hydrocarbons in the DP at the Prestige station in March 2006, indicates that the Prestige wrecks had been releasing oil for several years after the accident. However, despite the widespread occurrence of oil hydrocarbons in the three stations and throughout their water columns, it could not be concluded that the Prestige was the main source of pollution in the area near the Galician bank, which most likely has multiple origins. In fact, different water masses contain distinct contents of hydrocarbons in the SPM and the DP, which in some instances may have remote sources

Preparation and evaluation of sufficiently homogeneous and stable reference materials for priority hazardous substances in whole water

We have prepared and evaluated three whole water test materials containing eight polycyclic aromatic hydrocarbons (PAHs), six polybrominated diphenyl ethers (PBDEs) and tributyltin (TBT) with respect to homogeneity and short-term stability. The test materials were used as samples in two inter-laboratory comparisons. The materials were composed of natural mineral water and model suspended particulate matter (SPM) containing the target compounds at ng L-1 levels. The expanded uncertainty of the estimated mass concentrations in the final test materials was obtained by combining contributions from the homogeneity, the stability and the model-SPM characterization. The whole water materials were sufficiently homogeneous and stable at 4 °C for their intended use. Twelve out of fifteen investigated target parameters could be assessed to be present with a relative combined expanded uncertainty below 25 %. The outcome of the two inter-laboratory comparisons confirmed the good quality of the test materials and the level of uncertainties associated with the estimated mass concentrations. These findings are an important contribution towards the development of whole water matrix reference materials certified for PAH, PBDE and TBT in support of the Water Framework Directive of the European Union.JRC.D.2-Standards for Innovation and sustainable Developmen

Interaction of 15 priority substances for water monitoring at ng L-1 levels with glass-, aluminium- and fluorinated polyethylene bottles for the containment of water reference materials

Certified water reference materials (CRMs) are currently not available for most of the hydrophobic organic pollutants listed in the EU Water Framework Directive (WFD). To find the most suitable container type for subsequent reference material productions, feasibility studies for the preparation of waters with polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs) and tributyltin (TBT) close to Environmental Quality Standards (EQS) in water have been performed. Due to the hydrophobic nature of these compounds and their tendency to adsorb onto container-walls, an adequate selection of the most appropriate material for containment, storage and transport of water reference materials is crucial. Three different materials (aluminium, amber glass and fluorinated polyethylene, FPE) and three volume ranges (500/600 mL, 1000/1200 mL and 2000/3000 mL) were tested at ng L-1 level of the target compounds. FPE shows by far the highest loss of analytes due to adsorption onto the container walls for all compounds studied. Aluminium and glass are equally suited for PAHs and PBDEs, but aluminium is unsuitable as container material for TBT due to acid cleaning requirements. The volume of the containers had no dramatic effect on the adsorption behaviour of target compounds for the different volumes tested.JRC.D.2-Standards for Innovation and sustainable Developmen

Novel concepts for preparation of reference materials as whole water samples for priority substances at nanogram-per- liter level using model suspended particulate matter and humic acids

One of the unresolved issues of the European Water Framework Directive is the unavailability of realistic water reference materials for the organic priority pollutants at low ng L-1 concentrations. In the present study three different types of ready-to-use water test materials were developed for polycyclic aromatic hydrocarbons (PAHs), poly brominated diphenyl ethers (PBDEs) and tributyltin (TBT) at ng L-1 levels. The first type simulated the dissolved phase in the water and comprised of a solution of humic acids (HA) at 5 mg/L dissolved organic carbon (DOC) and a spike of the target compounds. The second type of water sample incorporated the particulate phase in water. To this end model suspended particulate matter (SPM) with a realistic particle size was produced by jet milling soil and sediments containing known amounts of PAHs, PBDEs and TBT and added as slurry to mineral water. The most complex test materials mimicked “whole water” consequently containing both phases, the model SPM and the HA solution with the target analytes strongly bound to the SPM. In this paper the development of concepts, processing of the starting materials, characterization of the HA and model SPMs as well as results for homogeneity and stability testing of the ready-to-use test materials are described in detail.JRC.D.2-Standards for Innovation and sustainable Developmen