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Fowles J.R.,Tox Logic Consulting | Banton M.I.,LyondellBasell | Boogaard P.J.,Royal Dutch Shell | Ketelslegers H.B.,ExxonMobil | Rohde A.M.,Concawe
Toxicology Letters | Year: 2016

The thyroid gland, and its associated endocrine hormones, is a growing area of interest in regulatory toxicology due to its important role in metabolism, growth and development. This report presents a review of the toxicology data on chemically complex petroleum streams for thyroid hormone effects.Toxicological summaries and studies from all available published and un-published sources were considered, drawing upon the European REACH regulatory submissions for 19 petroleum streams, with in depth review of 11 individual study reports and 31 published papers on related products or environmental settings. Findings relevant to thyroid pathology or thyroid hormone homeostasis were specifically sought, summarized, and discussed. A total of 349 studies of 28-days or longer duration were considered in the review, including data on mice, rats, rabbits, dogs, humans, and fish. The thyroid was almost invariably not a target organ in these studies. Three rodent studies did find thyroid effects; one on a jet fuel product (JP-8), and two studies on a heavy fuel oil product (F-179). The JP-8 product differs from other fuels due to the presence of additives, and the finding of reduced T4 levels in mice in the study occurred at a dose that is above that expected to occur in environmental settings (e.g. 2000 mg/kg). The finding for F-179 involved thyroid inflammation at 10-55 mg/kg that co-occurred with liver pathology in rats, indicating a possible secondary effect with questionable relevance to humans. In the few cases where findings did occur, the polycyclic aromatic hydrocarbon (PAH) content was higher than in related substances, and, in support of one possible adverse outcome pathway, one in-vitro study reported reduced thyroid peroxidase (TPO) activity with exposure to some PAH compounds (pyrene, benzo(k)fluoranthene, and benzo(e)pyrene). However, it could not be determined from the data available for this review, whether these specific PAH compounds were substantially higher in the JP-8 or F-179 products than in studies in which thyroid effects were not observed. Thus, a few products may carry a weak potential to affect the thyroid at high doses in rodents, possibly through secondary effects on the rodent liver or possibly through a pathway involving the inhibition of TPO by specific members of the PAH family.Human epidemiology evidence found weak and inconsistent effects on the thyroid but without identification of specific chemicals involved. Two studies in petroleum workers, which found a lower rate of morbidity and mortality overall, reported a statistically significant increase in thyroid cancer, but the small number of cases could not exclude confounding variables as possible explanations for the statistical findings.Overall, the available data indicates a low potential for thyroid hormone effects from exposure to petroleum streams, especially when the aromatic content is low. Because regulatory studies for most chemicals do not include detailed thyroid function or receptor studies, it remains possible that subclinical effects on this system may exist that were not detectable using conventional pathology or hormone measurements. © 2016 Elsevier Ireland Ltd.


Thomas A.O.,ERM | Leahy M.C.,ERM | Smith J.W.N.,Royal Dutch Shell | Spence M.J.,Concawe
Quarterly Journal of Engineering Geology and Hydrogeology | Year: 2017

Fatty acid methyl esters (FAME) are a group of organic compounds that can be synthesized through the process of esterification of fatty acids with methanol.With the increasing use of FAME in biodiesel, there is interest in the fate and effects of FAME in the environment. Single FAME compounds are of low aqueous solubility, low volatility and low mobility but the mechanisms of autoxidation and hydrolysis may result in the generation of more mobile but equally biodegradable components. The FAME types that have been studied in the peer-reviewed literature do not appear to enhance the solubility of hydrocarbons. FAME are widely reported to be readily biodegradable under both aerobic and anaerobic conditions, although rates may vary from site to site. In the majority of studies, biodiesel FAME biodegradation occurred more rapidly than petroleum diesel biodegradation. At sites with limited electron acceptors and macronutrients, microorganisms that degrade FAME have the potential to deplete available electron acceptors and nutrients, resulting in an extended time for diesel biodegradation. As with other labile biofuels, anaerobic biodegradation of FAME may result in significant methane generation. Overall, natural attenuation would appear to be significant in controlling the fate, behaviour and potential risks posed by biodiesel. © 2017 Concawe, Brussels.


Ketelslegers H.,Concawe | Rusyn I.,Texas A&M University | Kamelia L.,Wageningen University
CONCAWE Review | Year: 2017

Cat-App was initiated to minimize the need for testing in vertebrate animals under regulatory program. This is achieved by grouping petroleum substances (PS) to make the most optimal use of the toxicological information on PS by read-across of the available data within and between these groups. A framework will be developed for grouping based on chemical-biological properties combining multiple streams of information comprising PS production type/refining process, physical-chemical properties, chemical analytical profiles, existing (eco)toxicological data, and a comprehensive array of biological responses in a broad spectrum of in-vitro systems. Direct implementation of the Cat-App framework in the Concawe REACH strategy by applying the approach and submitting the data in the petroleum REACH dossiers will fill data gaps in the already-existing in-vivo toxicological data on PS, and help to develop a pragmatic and informed testing approach only as a last resort when read across to fill data gaps is not possible. This strategy will eventually address mandatory human health hazard end points under REACH while greatly reducing the use of vertebrate animals for toxicity testing without underestimating the potential hazards.


Demuynck J.,AECC | Favre C.,AECC | Bosteels D.,AECC | Hamje H.,Concawe | Andersson J.,Ricardo PLC
SAE Technical Papers | Year: 2017

The market share of Gasoline Direct Injection (GDI) vehicles has been increasing, promoted by its positive contribution to the overall fleet fuel economy improvement. It has however been reported that this type of engine is emitting more ultrafine particles than the Euro 6c Particle Number (PN) limit of 6·1011 particles/km that will be introduced in Europe as of September 2017 in parallel with the Real Driving Emission (RDE) procedure. The emissions performance of a Euro 6b GDI passenger car was measured, first in the OEM build without a Gasoline Particulate Filter (GPF) and then as a demonstrator with a coated GPF in the underfloor position. Regulated emissions were measured on the European regulatory test cycles NEDC and WLTC and in real-world conditions with Portable Emissions Measurement Systems (PEMS) according to the published European RDE procedure (Commission Regulation (EU) 2016/427 and 2016/646). Finally, tests were conducted on the chassis dyno to explore the impact of going towards the RDE boundary conditions (driving dynamics and ambient temperature as defined in the RDE legislation). PN results showed that the vehicle was a state-of-the-art GDI as values on the regulatory test cycles were below the Euro 6c limit of 6·1011 particles/km in its original configuration using the reference E5 fuel. A maximum value of 9·1011 particles/km was measured during the on-road tests, increasing to 2·1012 particles/km when going towards the RDE boundary conditions. With the GPF, PN emissions were controlled well below 6·1011 particles/km on NEDC, WLTC and on-road RDE. With GPF, emissions stayed well below 9·1011 particles/km towards the RDE boundaries, demonstrating that the GPF enables well controlled real-world PN emissions. No fuel penalty impact could be measured for the GPF during the tests and NOx emissions were always below the Euro 6d NTE (Not-to-exceed) limit that will apply from 2020 onwards. Copyright © 2017 SAE International.


PubMed | LTEC, ExxonMobil, Trent University and CONCAWE
Type: Journal Article | Journal: Journal of agricultural and food chemistry | Year: 2015

Components of emulsifiable concentrates (ECs) used in pesticide formulations may be emitted to air following application in agricultural use and contribute to ozone formation. A key consideration is the fraction of the ECs that is volatilized. This study is designed to provide a mechanistic model framework for estimating emissions of an aromatic hydrocarbon fluid used in ECs based on the results of spray chamber experiments that simulate fate as the fluids become subject to volatilization, sorption to soil, and biodegradation. The results indicate the need to treat the volatilization losses in three stages: (i) losses during spraying, (ii) losses up to 12 h after spraying in which the soil is coated with the ECs, and (iii) subsequent longer term losses in which the ECs become increasingly sorbed and subject to biodegradation. A mass balance model, the agrochemical derived volatile organic compound air transfer evaluation (ADVOCATE) tool, is developed, treating the ECs as seven hydrocarbon component groups, to estimate the volatilization and biodegradation losses using parameters fitted to empirical data. This enables losses to be estimated for each hydrocarbon component under field conditions, thereby providing a basis for improved estimation of ozone formation potential and for designing ECs that have lower emissions.


Christopher Y.,Institute of Occupational Medicine | Christopher Y.,University Utrecht | Van Tongeren M.,Institute of Occupational Medicine | Urbanus J.,CONCAWE | Cherrie J.W.,Institute of Occupational Medicine
Annals of Occupational Hygiene | Year: 2011

Heavy fuel oil (HFO) components are a group of heavy petroleum streams produced in oil refineries from crude oil. Due to its physicochemical properties, the dermal route is an important route of exposure. However, no information on dermal exposure levels for HFO has previously been published. A method for measuring dermal HFO levels was developed using wipe sampling and measuring phenanthrene and naphthalene as markers of HFO exposure. Measurement surveys were carried out in four different types of facilities: oil refineries, distribution terminals, energy providers, and an engine building and repair company. Dermal wipe samples were collected from different anatomical regions: neck, hands, and forearms. The frequency of tasks with potential for dermal HFO exposure was generally low at these facilities, with the exception of the distribution terminals and the engine building and repair site. The geometric mean (GM) dermal load on the hands was ∼0.1 μg cm -2 for both left and right hand and 0.013 and 0.019 μg cm -2 for the left and right forearm, respectively. With one exception, all results from the neck samples were below the limit of detection. The highest dermal loads for the hands and forearms were found in the engine building and repair facility (hands: GM = 1.6 μg cm -2; forearms: GM = 0.41 μg cm -2). The tasks with the highest dermal loads were the maintenance (hands: GM = 1.7 μg cm -2) and cleaning tasks (hands: GM = 0.24 μg cm -2). Actual dermal loads were low when compared with workplace dermal exposure measurements reported by other researchers for similar scenarios with other substances. This may be explained by high compliance of gloves use by workers during HFO handling tasks and likely avoidance of contact with HFO due to its high viscosity and the requirement to keep HFO at elevated temperatures during storage, transport, and use. © The Author 2010. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.


Comber M.H.I.,Mike Comber Consulting | Girling A.,Andrew Girling Environmental Consultant | den Haan K.H.,CONCAWE | Whale G.,Royal Dutch Shell
Integrated Environmental Assessment and Management | Year: 2015

The trend in discharges of petroleum-related substances from refineries in Europe shows a consistent picture of declining emissions, since first measured in 1969. This decline coincides with enhanced internal capture or recycling procedures and increasing use of physical and biological treatments. At the same time, and partly in response to legislative drivers, there has been an increase in the use of chronic (long-term) toxicity tests and alternative methods for assessing the quality of effluent discharges. The Whole Effluent Assessment (WEA) approach has also driven the increased conduct of studies addressing the fate of effluent constituents. Such studies have included the use of biodegradation and solid-phase micro-extraction-biomimetic extraction (SPME-BE) methods to address potentially bioaccumulative substances (PBS). In this way, it is then possible to address the persistence and toxicity of these PBS constituents of an effluent. The data collected in various case studies highlights the advantages and pitfalls of using biologically-based methods to assess the potential for refinery effluents to cause environmental impacts. Integr Environ Assess Manag 2015;X:000-000. ©2015 SETAC.


Leonards P.E.,VU University Amsterdam | Postma J.F.,Grontmij AquaSense | Comber M.,ExxonMobil | Whale G.,Royal Dutch Shell | Stalter G.,Concawe
Environmental Toxicology and Chemistry | Year: 2011

Whole effluent assessments (WEA) are being investigated as potential tools for controlling aqueous industrial discharges and minimizing environmental impact. The present study investigated how toxicity and the presence of potentially bioaccumulative substances altered when refinery effluents were subjected to biodegradation tests. Three petrochemical effluents were assessed, two freshwater and one saline, and subjected to two different types of biodegradation tests, resembling either a ready style (dissolved organic carbon (DOC)-die away) or an inherent style (Zahn-Wellens) test and the toxicity and potential to bioaccumulate parameters were re-analysed during and after biodegradation. A high proportion of the potentially bioaccumulative substances (PBS) in these effluents was easily biodegradable. Biodegradation not only lowered the PBS concentration but also toxicity. Appropriate controls are required however, as some increases in toxicity were observed after 4h. In the present study, six other petrochemical effluents were also assessed for their PBS content and toxicity to increase the understanding of the relationship between PBS and toxicity. The results showed that the PBS concentrations in these samples were lower than the estimated benchmarks of acute toxicity for algae, fish and crustacean, although two samples were above the critical PBS values for chronic narcotic toxicity for Daphnia magna, which support the assumption that narcotic effects are mainly responsible for the observed toxicity in refinery effluents. It can be concluded that for facilities processing petroleum products that the measurement of PBS is a suitable surrogate for toxicity tests at the screening stage. Finally, the combination of persistency, bioaccumulation, and toxicity tests was shown to have additional value compared to an approach using only toxicity tests. © 2011 SETAC.


PubMed | Royal Dutch Shell, ExxonMobil, Concawe, Tox Logic Consulting and LyondellBasell
Type: | Journal: Toxicology letters | Year: 2016

The thyroid gland, and its associated endocrine hormones, is a growing area of interest in regulatory toxicology due to its important role in metabolism, growth and development. This report presents a review of the toxicology data on chemically complex petroleum streams for thyroid hormone effects. Toxicological summaries and studies from all available published and un-published sources were considered, drawing upon the European REACH regulatory submissions for 19 petroleum streams, with in depth review of 11 individual study reports and 31 published papers on related products or environmental settings. Findings relevant to thyroid pathology or thyroid hormone homeostasis were specifically sought, summarized, and discussed. A total of 349 studies of 28-days or longer duration were considered in the review, including data on mice, rats, rabbits, dogs, humans, and fish. The thyroid was almost invariably not a target organ in these studies. Three rodent studies did find thyroid effects; one on a jet fuel product (JP-8), and two studies on a heavy fuel oil product (F-179). The JP-8 product differs from other fuels due to the presence of additives, and the finding of reduced T4 levels in mice in the study occurred at a dose that is above that expected to occur in environmental settings (e.g. 2000mg/kg). The finding for F-179 involved thyroid inflammation at 10-55mg/kg that co-occurred with liver pathology in rats, indicating a possible secondary effect with questionable relevance to humans. In the few cases where findings did occur, the polycyclic aromatic hydrocarbon (PAH) content was higher than in related substances, and, in support of one possible adverse outcome pathway, one in-vitro study reported reduced thyroid peroxidase (TPO) activity with exposure to some PAH compounds (pyrene, benzo(k)fluoranthene, and benzo(e)pyrene). However, it could not be determined from the data available for this review, whether these specific PAH compounds were substantially higher in the JP-8 or F-179 products than in studies in which thyroid effects were not observed. Thus, a few products may carry a weak potential to affect the thyroid at high doses in rodents, possibly through secondary effects on the rodent liver or possibly through a pathway involving the inhibition of TPO by specific members of the PAH family. Human epidemiology evidence found weak and inconsistent effects on the thyroid but without identification of specific chemicals involved. Two studies in petroleum workers, which found a lower rate of morbidity and mortality overall, reported a statistically significant increase in thyroid cancer, but the small number of cases could not exclude confounding variables as possible explanations for the statistical findings. Overall, the available data indicates a low potential for thyroid hormone effects from exposure to petroleum streams, especially when the aromatic content is low. Because regulatory studies for most chemicals do not include detailed thyroid function or receptor studies, it remains possible that subclinical effects on this system may exist that were not detectable using conventional pathology or hormone measurements.


PubMed | Royal Dutch Shell, Mike Comber Consulting, CONCAWE and Andrew Girling Environmental Consultant
Type: Journal Article | Journal: Integrated environmental assessment and management | Year: 2015

The trend in discharges of petroleum-related substances from refineries in Europe shows a consistent picture of declining emissions, since first measured in 1969. This decline coincides with enhanced internal capture or recycling procedures and increasing use of physical and biological treatments. At the same time, and partly in response to legislative drivers, there has been an increase in the use of chronic (long-term) toxicity tests and alternative methods for assessing the quality of effluent discharges. The Whole Effluent Assessment (WEA) approach has also driven the increased conduct of studies addressing the fate of effluent constituents. Such studies have included the use of biodegradation and solid-phase micro-extraction-biomimetic extraction (SPME-BE) methods to address potentially bioaccumulative substances (PBS). In this way, it is then possible to address the persistence and toxicity of these PBS constituents of an effluent. The data collected in various case studies highlights the advantages and pitfalls of using biologically-based methods to assess the potential for refinery effluents to cause environmental impacts.

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