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Redman A.D.,ExxonMobil | Parkerton T.F.,ExxonMobil | Comber M.H.,University of Exeter | Paumen M.L.,ExxonMobil | And 6 more authors.
Integrated Environmental Assessment and Management | Year: 2014

PETRORISK is a modeling framework used to evaluate environmental risk of petroleum substances and human exposure through these routes due to emissions under typical use conditions as required by the European regulation for the Registration, Evaluation, Authorization and Restriction of Chemicals (REACH). Petroleum substances are often complex substances comprised of hundreds to thousands of individual hydrocarbons. The physicochemical, fate, and effects properties of the individual constituents within a petroleum substance can vary over several orders of magnitude, complicating risk assessment. PETRORISK combines the risk assessment strategies used on single chemicals with the hydrocarbon block approach to model complex substances. Blocks are usually defined by available analytical characterization data on substances that are expressed in terms of mass fractions for different structural chemical classes that are specified as a function of C number or boiling point range. The physicochemical and degradation properties of the blocks are determined by the properties of representative constituents in that block. Emissions and predicted exposure concentrations (PEC) are then modeled using mass-weighted individual representative constituents. Overall risk for various environmental compartments at the regional and local level is evaluated by comparing the PECs for individual representative constituents to corresponding predicted no-effect concentrations (PNEC) derived using the Target Lipid Model. Risks to human health are evaluated using the overall predicted human dose resulting from multimedia environmental exposure to a substance-specific derived no-effect level (DNEL). A case study is provided to illustrate how this modeling approach has been applied to assess the risks of kerosene manufacture and use as a fuel. © 2014 SETAC.


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.


Daines K.,Arcadis | Dow R.,Arcadis | Lethbridge G.,Royal Dutch Shell | Smith J.W.N.,Royal Dutch Shell | And 2 more authors.
Quarterly Journal of Engineering Geology and Hydrogeology | Year: 2011

Releases of hydrocarbon-based fuels at retail filling stations have the potential to affect soil and groundwater and are listed by the European Commission as a potential pressure on achievement of the Water Framework Directive's water quality objectives. This paper presents an analysis of the environmental sensitivity of retail filling station locations across Europe, with regard to proximity to groundwater, surface water and ecological receptors. A geographic information system-based approach was used to map the location of nearly 86 000 retail filling station sites to zones of differing environmental sensitivity. The results indicate that the environmental sensitivity of retail filling stations is highly variable, and that only a relatively small proportion has the potential to cause impact on groundwater abstractions, surface water or to designated ecological receptors. Accordingly, a sitespecific risk-based approach to the design and operation of retail filling stations provides the most proportionate and sustainable basis for their management. In addition, the research provides a tool for both single retail filling station operators and the oil industry as a whole to identify areas of higher environmental sensitivity, encouraging the focusing of investment in preventive measures where it is most needed. © 2011 Geological Society of London.


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.


Rose K.D.,Concawe | Samaras Z.,Aristotle University of Thessaloniki | Jansen L.,Kuwait | Clark R.,Royal Dutch Shell | And 7 more authors.
SAE International Journal of Fuels and Lubricants | Year: 2010

Fatty Acid Methyl Ester (FAME) products derived from vegetable oils and animal fats are now widely used in European diesel fuels and their use will increase in order to meet mandated targets for the use of renewable products in road fuels. As more FAME enters the diesel pool, understanding the impact of higher FAME levels on the performance and emissions of modern light-duty diesel vehicles is increasingly important. Of special significance to Well-to-Wheels (WTW) calculations is the potential impact that higher FAME levels may have on the vehicle's volumetric fuel consumption. The primary objective of this study was to generate statistically robust fuel consumption data on three light-duty diesel vehicles complying with Euro 4 emissions regulations. These vehicles were evaluated on a chassis dynamometer using four fuels: A hydrocarbon-only diesel fuel and three FAME/diesel fuel blends containing up to 50% v/v FAME. One FAME type, a Rapeseed Methyl Ester (RME), was used throughout. One vehicle was equipped only with an oxidation catalyst while the other two were also equipped with two types of Diesel Particulate Filters (DPFs). In addition to CO 2 emissions, regulated tailpipe emissions (NOx, HC, CO, PM, and PN) were collected in order to evaluate the impact of higher RME contents on emissions performance. The results obtained over the New European Driving Cycle (NEDC) indicate that the volumetric fuel consumption systematically increases with increasing RME content for all three vehicles. Within the statistical precision, the vehicles were not able to compensate for the lower energy content of the RME/diesel blends and consumed more fuel in direct proportion to the lower energy content of the RME/diesel blends. As the RME content of the fuel increased, the particulate mass (PM) and solid particle number (PN) were generally found to decrease over the NEDC while the NOx, CO, and HC emissions increased. The overall impact of RME on regulated tailpipe emissions is much smaller, however, compared to the variations in emissions seen over the NEDC sub-cycles. © 2010 SAE International.


Stradling R.,Royal Dutch Shell | Rickeard D.,Concawe | Hamje H.,Concawe | Williams J.,BP International Ltd | Zemroch P.,Royal Dutch Shell
SAE Technical Papers | Year: 2015

The performance aspect of gasoline combustion has traditionally been measured using Research Octane Number (RON) and Motor Octane Number (MON) which describe antiknock performance under different conditions. Recent literature suggests that MON is less important than RON in modern cars and a relaxation in the MON specification could improve vehicle performance, while also helping refiners in the production of gasoline. At the same time, for the same octane number change, increasing RON appears to provide more benefit to engine power and acceleration than reducing MON. It has also been suggested that there could be fuel efficiency benefits (on a tank to wheels basis) for specially adapted engines, for example, operating at higher compression ratio, on very high RON (100+). Other workers have advocated the use of an octane index (OI) which incorporates both RON and MON to give an indication of octane quality. The objective of this study was to investigate the effect of RON and MON on the power and acceleration performance of two Euro 4 gasoline vehicles under full throttle acceleration conditions. Fifteen fuels covering RON levels 95 to 103 and sensitivities (RON minus MON) up to 15 were blended and tested. Both pure hydrocarbon and blends containing ethanol or ETBE were included so that any specific effects of oxygenates could be identified. Three additional fuels, covering RON as low as 86, were blended using primary reference fuels. The results confirm the findings of other studies that MON is not a good predictor of vehicle performance and in fact high MON levels increase acceleration time under full throttle conditions. Copyright © 2015 SAE International.


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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