Screening Assessment

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Petroleum Sector Stream Approach
Heavy Fuel Oils
[Site-Restricted]

Chemical Abstracts Service Registry Numbers
64741-45-3
64741-61-3
64741-80-6
68333-22-2
68333-27-7
68476-32-4
68478-17-1

Environment Canada
Health Canada

September 2011

(PDF Version - 1,319 KB)

Table of Contents

• Synopsis
• Introduction
• Substance Identity
• Physical and Chemical Properties
• Sources
• Uses
• Releases to the Environment
• Environmental Fate
• Persistence and Bioaccumulation Potential
• Potential to Cause Ecological Harm
• Potential to Cause Harm to Human Health
• Conclusion
• References
• Appendix 1: Description of the Nine Groups of Petroleum Substances
• Appendix 2: Engineering Process Flow Diagrams for Heavy Fuel Oils
• Appendix 3: Data Tables for Site-restricted HFOs
• Appendix 4: Summary of Health Effects Information from Pooled Toxicological Data for HFO Substance

Synopsis

The Ministers of the Environment and of Health have conducted a screening assessment of the following site-restricted heavy fuel oils (HFOs):

^[a] The Chemical Abstracts Service Registry Number (CAS RN) is the property of the American Chemical Society and any use or redistribution, except as required in supporting regulatory requirements and/or for reports to the government when the information and the reports are required by law or administrative policy, is not permitted without the prior, written permission of the American Chemical Society.
^[b] DSL = Domestic Substances List

These substances were identified as high priorities for action during the categorization of the Domestic List, as they were determined to present the greatest potential or intermediate potential for exposure of individuals in Canada and were considered to present a high hazard to human health. Most of these substances were identified by categorization as ecological priorities as some of their components met criteria for persistence or bioaccumulation and inherent toxicity to non-human organisms, but no components met all three criteria. These substances were all included in the Petroleum Sector Stream Approach (PSSA) because they are related to the petroleum sector and are all complex mixtures.

Heavy fuel oils (HFOs) are a group of complex petroleum mixtures that serve as blending stocks in final heavy fuel products or as intermediate products of distillate or residue derived from refinery distillation or cracking units. The final fuel product usually consists of a mixture of HFOs as well as higher-quality hydrocarbons as diluents. HFOs are composed of aromatic, aliphatic and cycloalkane hydrocarbons, primarily in the carbon range of C₂₀ to C₅₀ (C₁₁ is the smallest hydrocarbon found in the group) and have a typical boiling point range from 160–650°C. As such, HFOs are considered to be of Unknown or Variable composition, Complex reaction products or Biological materials (UVCBs). In order to predict the overall behaviour of these complex substances for the purposes of assessing the potential for ecological effects, representative structures have been selected from each chemical class in the mixture.

Based on the combined evidence of empirical and modeled bioconcentration/ bioaccumulation potential, the HFOs assessed in this report likely contain large proportions of C₁₅-C₂₀ components that are highly bioaccumulative based on criteria in the Persistence and Bioaccumulation Regulations of CEPA 1999. All of the HFOs considered here may be comprised of significant proportions of components (mostly ≥C₃₀) that persist in soil, water and sediments based on criteria in the Persistence and Bioaccumulation Regulations. No components of these HFOs were found to be both persistent and bioaccumulative based on criteria in the Persistence and Bioaccumulation Regulations.

The modelled ecotoxicological data suggest that these HFOs, as complex mixtures, are potentially hazardous to aquatic organisms. However, the HFOs considered in this report have been identified as site-restricted (i.e., they are a subset of HFOs that are not expected to be transported off of the petroleum refinery or upgrader facility sites). Accordingly, exposure is expected to be negligible and so the potential for ecological harm is considered to be low.

Site-restricted HFOs were identified as a high priority for action because they were considered to present a high hazard to human health. A critical effect for the initial categorization of site-restricted HFO substances was carcinogenicity, based primarily on classifications by international agencies. Several studies reported skin tumour development in mice, rabbits and monkeys following repeated dermal application of HFO substances. HFOs demonstrated genotoxicity in in vivo and in vitro assays, although results varied between HFOs with different CAS RNs. Studies on laboratory animals indicate that HFOs may also adversely affect reproduction and development. Information on additional HFO substances in the PSSA that are similar from a processing and physical-chemical perspective were considered for characterization of human health effects.

The HFOs considered in this screening assessment have been identified as site-restricted. According to information submitted under section 71 of CEPA 1999 and other sources of information, these HFOs are consumed on site or blended into substances leaving the site under different CAS RNs. In addition, a number of regulatory and non-regulatory measures are already in place in Canada, which minimize releases of site-restricted petroleum sector substances, including provincial/territorial operating permit requirements, and best practices and guidelines put in place by the petroleum industry at refinery and upgrader facilities. Accordingly, environmental and general population exposure to these substances is not expected, and therefore harm to the environment or human health is not expected.

Therefore, it is concluded that these site-restricted HFO substances are not entering the environment in a quantity or concentration or under conditions that have or may have an immediate or long-term harmful effect on the environment or its biodiversity, or that constitute or may constitute a danger to the environment on which life depends, or that constitute a danger in Canada to human life or health.

Based on the information available, it is concluded that the seven site-restricted HFOs listed under CAS RNs 64741-45-3, 64741-61-3, 64741-80-6, 68333-22-2, 68333-27-7, 68476-32-4 and 68478-17-1 do not meet any of the criteria set out in section 64 of CEPA 1999.

Because these substances are listed on the Substances List, their import and manufacture in Canada are not subject to notification under subsection 81(1) of CEPA 1999. Given the potential hazardous properties of these substances, there is concern that new activities that have not been identified or assessed could lead to these substances meeting the criteria set out in section 64 of the Act. Therefore, application of the Significant New Activity provisions of the Act to these substances is being considered, so that any proposed new manufacture, import or use of this substance outside a petroleum refinery or upgrader facility is subject to further assessment, to determine if the new activity requires further risk management consideration.

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Introduction

The Canadian Environmental Protection Act, 1999 (CEPA 1999) (Canada 1999) requires the Minister of the Environment and the Minister of Health to conduct screening assessments of substances that have met the categorization criteria set out in the Act to determine whether these substances present or may present a risk to the environment or to human health.

Based on the information obtained through the categorization process, the Ministers identified a number of substances as high priorities for action. These include substances that:

• met all of the ecological categorization criteria, including persistence (P), bioaccumulation potential (B) and inherent toxicity to aquatic organisms (iT), and were believed to be in commerce in Canada; and/or
• met the categorization criteria for greatest potential for exposure (GPE) or presented an intermediate potential for exposure (IPE) and had been identified as posing a high hazard to human health based on classifications by other national or international agencies for carcinogenicity, genotoxicity, developmental toxicity or reproductive toxicity.

A key element of the Government of Canada’s Chemicals Management Plan (CMP) is the Petroleum Sector Stream Approach (PSSA), which involves the assessment of approximately 160 petroleum substances that are considered high priorities for action. These substances are primarily related to the petroleum sector and are considered to be of Unknown or Variable composition, Complex reaction products or Biological materials (UVCBs).

Screening assessments focus on information critical to determining whether a substance meets the criteria as set out in section 64 of CEPA 1999. Screening assessments examine scientific information and develop conclusions by incorporating a weight-of-evidence approach and precaution.^[1]

Grouping of Petroleum Substances

The high priority petroleum substances fall into nine groups of substances based on similarities in production, toxicity and physical-chemical properties (Table A1.1 in Appendix 1). In order to conduct screening assessments, each high priority petroleum substance was placed into one of five categories (“streams”) based on its production and use in Canada:

An analysis of the available data determined that approximately 70 high priority petroleum substances are site-restricted under stream 1, as described above. These occur within four of the nine substance groups: heavy fuel oils, gas oils, petroleum and refinery gases, and low boiling point naphthas.

These site-restricted substances were identified as GPE or IPE during the categorization exercise based on their production volumes reported in the Domestic Substances List (DSL). However, according to information submitted under section 71 of CEPA 1999, voluntary industry submissions, an in-depth literature review, and a search of material safety data sheets, these substances are consumed on-site or are blended into substances leaving the site under different Chemical Abstract Services Registry Numbers (CAS RNs) (which will also be addressed under the CMP).

This screening assessment addresses seven site-restricted heavy fuel oils (HFOs) described under CAS RNs 64741-45-3, 64741-61-3, 64741-80-6, 68333-22-2, 68333-27-7, 68476-32-4 and 68478-17-1. The remaining high priority HFOs (under 14 different CAS RNs) will be assessed separately as they belong to streams 2, 3 or 4 (as described above). Health effects were assessed using toxicological data pooled across all 21 HFO CAS RNs.

Included in this screening assessment is the consideration of information on chemical properties, hazards, uses and exposure, including the additional information submitted under section 71 of CEPA 1999. Data relevant to the screening assessment of these substances were identified in original literature, review and assessment documents, stakeholder research reports and from recent literature searches, up to July 2010 for the environmental components of the document and up to October 2009 for the health components. Key studies were critically evaluated; modelling results were used to reach conclusions.

Characterizing risk to the environment involves the consideration of data relevant to environmental behaviour, persistence, bioaccumulation and toxicity, combined with an estimation of exposure to potentially affected non-human organisms from the major sources of release to the environment. Conclusions regarding risk to the environment are based in part on an estimation of environmental concentrations resulting from releases and the potential for these concentrations to have a negative impact on non-human organisms. As well, other lines of evidence of environmental hazard are taken into account. The ecological portion of the screening assessment summarizes the most pertinent data on environmental behaviour and effects, and does not represent an exhaustive or critical review of all available data. Environmental models and comparisons with similar petroleum mixtures may assist in the assessment.

Evaluation of risk to human health involves consideration of data relevant to estimation of exposure (non-occupational) of the general population, as well as information on health hazards (based principally on the weight of evidence assessments of other agencies that were used for prioritization of the substance). Decisions for human health are based on the nature of the critical effect and/or margins between conservative effect levels and estimates of exposure, taking into account confidence in the completeness of the identified databases on both exposure and effects, within a screening context. The screening assessment does not represent an exhaustive or critical review of all available data. Rather, it presents a summary of the critical information upon which the conclusion is based.

This screening assessment was prepared by staff in the Existing Substances Programs at Health Canada and Environment Canada and incorporates input from other programs within these departments. The human health and ecological portions of this assessment have undergone external written peer review/consultation. Comments on the technical portions relevant to human health were received from scientific experts selected and directed by Equilibrium Environmental Inc., including Anthony Knafla (Equilibrium Environmental Inc) and Ross Wilson (Wilson Scientific Consulting Inc.).

Additionally, the draft of this screening assessment was subject to a 60-day public comment period. While external comments were taken into consideration, the final content and outcome of the screening assessment remain the responsibility of Health Canada and Environment Canada.

The critical information and considerations upon which the screening assessment is based are summarized below.

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Substance Identity

Heavy fuel oils (HFOs) are a group of complex petroleum mixtures that serve as blending constituents in final fuel products or as intermediate products of distillate or residue derived from refinery distillation or cracking units (Table A3.1 in Appendix 3) (CONCAWE 1998). The final fuel product usually consists of a blend of HFOs and high-quality hydrocarbons that have been produced in the refinery or in upgrader facilities.

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Physical and Chemical Properties

The composition and physical-chemical properties of HFOs vary based on the source of crude oil or bitumen, and the processing steps involved. A summary of data on the physical and chemical properties of site-restricted HFOs is presented in Table 1.

HFOs are composed of aromatic, aliphatic and cycloalkane hydrocarbons, primarily in the carbon range of C₁₁ to C₅₀ (Table A3.1 in Appendix 3) (CONCAWE 1998) and have a general boiling-point range of 160–650°C (API 2004).

Table 1: General physical and chemical properties for site-restricted HFOs

Abbreviations: K_oc, organic carbon–water partition coefficient; K_ow, octanol-water partition coefficient.
^[*] Boiling-point ranges are not known for all CAS RNs in this report; this is a general range for HFOs.

The theoretical vapour pressures of individual substances comprising HFOs are low to moderate due to their high molecular weights. However, the actual vapour pressures will be influenced by the substance composition of the HFO mixture in which they occur. Water solubilities of all HFOs are low and octanol-water partition coefficient estimations vary considerably, probably due to the complex nature of these mixtures.

In order to predict the overall properties and behaviour of a complex petroleum substance, representative structures were selected from each chemical class within the mixture. Thirty structures were chosen based on boiling-point ranges for each HFO (Table A3.2 in Appendix 3), the amount of data on each structure, and the median of the boiling-point range of similar structures. The database in PetroTox (2009) was used to select representative structures. As the precise substance compositions of HFOs are not well defined and are indeed variable, representative structures are not considered to be proportionally representative. This resulted in the selection of representative structures for alkanes, isoalkanes, 1- and 2-ring cycloalkanes, and one-, two-, three- and five-ring aromatics ranging from C₁₅ to C₅₀ (Table A3.3 in Appendix 3). Physical-chemical data for each representative structure were assembled from the scientific literature or from the EPIsuite (2008) group of environmental models. No information was found on the boiling point or carbon range of CAS RN 68476-32-4; therefore, it is unclear what structures would be representative. However, its properties likely reflect the properties of the other site-restricted HFOs, and this is assumed throughout.

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Sources

Site-restricted HFOs are produced in Canadian refineries and upgraders. The CAS RN descriptions (NCI 2006), typical process flow diagrams (Figures A2.1 to A2.7b in Appendix 2) (Hopkinson 2008), and information collected under section 71 of CEPA 1999 (Environment Canada 2008, 2009), indicate that these substances are intermediate streams within both refineries and upgraders or are blended to make other products under a new CAS RN. As such, these HFOs are not expected to be transported off of facility sites. Consequently, the quantities produced are not critical to this screening assessment since the potential for release to the environment is negligible.

CAS RN 64741-45-3 represents a residual fraction from atmospheric distillation of crude oils (Figure A2.1 in Appendix 2).

CAS RN 64741-61-3 represents a distillate derived from a fractionation column treated with the effluent from a catalytic cracking process (Figure A2.2 in Appendix 2).

CAS RN 64741-80-6 refers to a residual fraction derived from fractionating a mixture produced from a thermal cracking process (e.g., coking or visbreaking) (Figure A2.3 in Appendix 2).

CAS RN 68333-22-2 refers to a residual fraction from atmospheric distillation of crude oils (Figure A2.4 in Appendix 2).

CAS RN 68333-27-7 represents a residual fraction from the bottom of a distillation column fed with hydrogen-treated intermediate distillate from a catalytic cracking unit (Figure A2.5 in Appendix 2).

CAS RN 68476-32-4 represents several streams direct from the atmospheric distillation tower to kerosene/diesel blending (Figure A2.6 in Appendix 2).

CAS RN 68478-17-1 refers to a residual fraction from a distillation column treated with heavy coker gas oil and/or vacuum gas oil derived from a coking unit and/or a vacuum distillation unit in a refinery or an upgrader (Figures A2.7a and A2.7b in Appendix 2).

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Uses

According to the information collected through the Notice with respect to certain high priority petroleum substances (Environment Canada 2008) and the Notice with respect to potentially industry-limited high priority petroleum substances (Environment Canada 2009), published under section 71 of CEPA 1999, the substances listed in this screening assessment were identified as either being consumed at the facility or blended into substances leaving the site under different CAS RNs. Although these substances were identified by multiple use-codes established during the development of the DSL, it has been determined from information submitted under section 71 of CEPA 1999 (Environment Canada 2008, 2009), voluntary submissions from industry, an in-depth literature review and a search of material safety data sheets that these site-restricted HFOs are not expected to be transported off refinery or upgrader facility sites.

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Releases to the Environment

Potential releases of HFO substances from refineries and upgraders can be characterized as either controlled or unintentional releases. Controlled releases are planned releases from pressure relief valves, venting valves and drain systems that occur for safety purposes or maintenance, considered part of routine operations, and occur under controlled conditions. Unintentional releases are typically characterized as unplanned releases due to spills or leaks from various equipment, seals, valves, pipelines, flanges, etc., resulting from equipment failure, poor maintenance, lack of proper operating practices, adverse weather conditions or other unforeseen factors. Refinery and upgrader operations are highly regulated and regulatory requirements are established under various jurisdictions. As well, voluntary non-regulatory measures implemented by the petroleum industry are in place to manage these releases (SENES 2009).

Controlled Releases

The site-restricted HFO CAS RNs in this screening assessment originate from distillation columns in a refinery or an upgrader, either as a residue (bottom product) or a distillate. Thus, the potential locations for the controlled release of HFOs include relief valves and venting valves or drain valves on the piping or (e.g., vessels) in the vicinity of this equipment.

Under typical operating conditions, controlled releases of site-restricted HFOs would be captured in a closed system[3], according to defined procedures, and returned to the processing facility or to the facility wastewater treatment plant. In both cases, exposure of the general population or the environment is not expected from the site-restricted HFO substances under the CAS RNs identified in this screening assessment as they are not expected to be transported off refinery or upgrader facility sites.

Unintentional Releases

Unintentional releases (including fugitive releases) occur from equipment (e.g., pumps, storage tanks), seals, valves, piping, flanges, etc., during processing and handling of petroleum substances and can be greater in situations of poor maintenance or operating practice. Regulatory and non-regulatory measures are in place to reduce these events at petroleum refineries and upgraders (SENES 2009). Rather than being specific to one substance, these measures are developed in a more generic way in order to reduce unintentional releases of all substances in the petroleum sector.

For the Canadian petroleum industry, requirements at the provincial or territorial level typically prevent or manage the unintentional releases of petroleum substances and streams within a facility (through the use of operating permits) (SENES 2009).

At the federal level, unintentional releases of some petroleum substances are addressed under the Fisheries Act; the Petroleum Refinery Liquid Effluent Regulations and Guidelines set the discharge limits of oil and grease, phenol, sulphides, ammonia nitrogen and total suspended matter, as well as testing requirements for acute toxicity in the final petroleum effluents entering Canadian waters.

Additionally, existing occupational health and safety legislation specifies measures to reduce occupational exposures of employees, and some of these measures also serve to reduce unintentional releases (CanLII 2009).

Non-regulatory measures (e.g., guidelines, best practices) to reduce unintentional releases at petroleum-sector facilities include appropriate material selection during the design and setup processes, regular inspection and maintenance of storage tanks, pipelines and other process equipment, the implementation of leak detection and repair or other equivalent programs, the use of floating roofs in aboveground storage tanks to reduce the internal gaseous zone and the minimal use of underground tanks, which can lead to undetected leaks (SENES 2009).

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Environmental Fate

Since all of the available information indicates that these site-restricted HFOs are not transported or released from refinery or upgrader sites into the environment, only general data on the environmental behaviour of these substances is presented in the screening assessment.

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Persistence and Bioaccumulation

Environmental Persistence

No empirical data are available on the degradation of these site-restricted HFOs as complex mixtures. A quantitative structure-activity relationship (QSAR)-based weight of evidence approach (Environment Canada 2007) was therefore applied using the BioHCwin (2008), BIOWIN (2008) and AOPWIN (2008) degradation models. Modelling was based on the various representative structures of the HFOs.

AOPWIN (2008) is a model that calculates atmospheric oxidation half-lives of compounds in contact with hydroxyl radicals in the troposphere under the influence of sunlight. Atmospheric oxidation rates were calculated for all of the representative structures. Although the low vapour pressures of these representative structures indicate that volatilization may not be a very significant fate process, oxidation half-lives less than 1 day (Table A3.11 in Appendix 3) indicate this would be a relatively rapid removal process if these substances were introduced into the atmosphere (Atkinson 1990; API 2004).

Based on the analysis of ultimate biodegradation in water from the BIOWIN (2008) model, and primary biodegradation in water from the BioHCwin (2008) model, the C₃₁ to C₅₀ alkanes, C₃₀ to C₅₀ isoalkanes, C₃₅ to C₅₀ one-ring cycloalkanes, C₂₀ to C₅₀ two-ring cycloalkanes, C₃₀ to C₅₀ one-ring aromatics, C₄₂ to C₅₀two-ring aromatics, C₃₀ to C₅₀ three-ring aromatics, and C₂₀ to C₃₀ five-ring PAHs in these HFOs all have half-lives in water ≥ 182 days (Table A3.4 in Appendix 3). Using an extrapolation ratio of 1:1:4 for water:soil:sediment biodegradation half-lives (Boethling et al. 1995), the half-lives in soil and sediment can be extrapolated from the half-life estimations in water. This extrapolation indicates that many of the mid and all of the high molecular weight components would have half-lives of ≥ 182 days in soil and ≥ 365 days in sediment.

All of the HFOs considered in this report contain significant proportions of components (mostly ≥C₃₀; see Table A3.5 in Appendix 3) that are persistent based on criteria in the Persistence and Bioaccumulation Regulations (Canada 2000).

Potential for Bioaccumulation

Since no experimental bioaccumulation or bioconcentration data for these HFOs as a mixture were available, empirical data on representative structures found in HFOs and other hydrocarbon mixtures in a read-across approach, and a predictive approach using a bioconcentration factor (BCF) model, were applied (BCFBAF 2008a). The BCFBAF model incorporates the generic QSAR model of Arnot and Gobas (2003).

Uptake and depuration of various petroleum hydrocarbons by mollusks and fishes has been shown in numerous studies (Stegeman and Teal 1973; Hardy et al. 1974; Fong 1976; Roubal et al. 1978; McCain et al. 1978; Nunes and Benville 1978; Cravedi and Tulliez 1983; Niimi and Palazzo 1986; Niimi and Dookhran 1989; Hellou et al. 1994; Burkhard and Lukasewycz 2000; Wetzel and van Vleet 2004; Colombo et al. 2007; Zhou et al. 1997). Aromatic and aliphatic components are readily taken up, primarily in adipose tissue. Moderate concentrations have been found in muscle, gall bladder, gill and brain of exposed fish, but once these fish were removed to a clean environment, depuration occurs. However, tissue levels can remain relatively constant for a period of time. It may take weeks to months to reach undetectable levels. After a spill, the pollution load may remain for some time in the natural environment; therefore, the time for depuration in fish will be longer than that reported in laboratory-controlled studies.

Due to the lack of a rapid detoxification system, mollusks are unable to metabolize aromatic hydrocarbons readily. Moderate accumulation of petroleum hydrocarbons can occur in stable tissue compartments with low hydrocarbon turnover (Stegeman and Teal 1973; Neff et al. 1976).

It is reported that bioaccumulation of petroleum hydrocarbons in higher-chain organisms such as fish is found to be low due to their metabolic elimination and detoxification mechanisms (Southworth et al. 1978; Jonsson et al. 2004). There is no evidence that petroleum hydrocarbons biomagnify up the food chain (Broman et al. 1990; Wan et al. 2007; Takeuchi et al. 2009).

Only three studies on bioaccumulation factors (BAFs) of PAHs in aquatic organisms (fish and clams) were found (Neff et al. 1976; Zhou et al. 1997; Burkhard and Lukasewyez 2000). The PAHs studied were one-ring C₆ to C₉, two-ring C₁₀ to C₁₃ and three-ring C₁₄ to C₁₈. As reflected by the findings of Niimi and Dookhran (1989) and Niimi and Palazzo (1986), PAHs were not accumulated by fish through dietary exposure because of the combined effects of poor absorption efficiencies and rapid elimination rates. Hence, none of the measured BAFs for one-ring aromatics and PAHs in the carbon range C₆ to C₁₈ were considered to be high.

For bioaccumulation, the derivation of a bioaccumulation factor (BAF) is preferred over a bioconcentration factor (BCF), because the latter does not include chemical exposure through diet (Barron 1990). However, due to the scarcity of measured BAFs available, BCFs from various published works were compiled to provide further evidence for bioaccumulation and BAFs were predicted using kinetic mass-balance modeling (Arnot and Gobas 2003).

A suite of BCFs for components of heavy fuel oils (C₆ to C₁₈) were found (Table A3.7 in Appendix 3), namely for: alkanes, isoalkanes, two-ring cycloalkanes, two-ring cycloalkanes, one-ring aromatics, cycloalkane monoaromatics, cycloalkane diaromatic, and polyaromatics (Carlson et al. 1979; CITI 1992; Tolls and van Dijk 2002; Jonsson et al. 2004; Yakata et al. 2006; EMBSI 2004, 2005a, b, 2006, 2007, 2008f, 2009; JNITE 2010). Of the 31 components studied, only a C₁₃ two-ring aromatic, 2-isopropyl naphthalene had a BCF > 5000. However, this isopropyl functional group was considered to be atypical of petroleum hydrocarbons (Lampi et al. 2010). The remaining measured BCF show that this fraction is not expected to highly bioconcentrate in fish via water-borne exposures (Table A3.7 Appendix 3).

The BCF and BAF model estimates for the 11 C₁₅ to C₂₀ linear and cyclic representative structures range from 219–470 000 (Table A3.6 in Appendix 3). There are no measured BCF or BAF data for this particular carbon fraction. Only the C₁₅ two ring cycloalkanes were predicted to have a BCF greater than 5000 suggesting a lower potential for uptake from the water for this carbon range in general. However, the carbon range around C₁₅ appear to be highly bioaccumulative via the diet as most of the BAFs predicted for the cycloalkane and aromatic components in this carbon fraction exceed 5000 (Tables A3.6 in Appendix 3). The BCF and BAF predictions for the C₁₅ fraction are within the parametric, mechanistic and metabolic domains of the model and so are considered reliable.

Most components > C₂₀ have an estimated log K_ow > 8 and were excluded from the modeling, as predictions may be highly uncertain due to limitations of the model (Arnot and Gobas 2003). In Arnot and Gobas (2006a), at a log K_ow of 8.0, the empirical distribution of “acceptable” fish BCF data shows that there are very few chemicals with fish BCFs exceeding 5000. Examination of Environment Canada’s empirical BCF/BAF database for DSL and non-DSL chemicals developed by Arnot and Gobas (2003b) and further by Arnot (2005, 2006b) shows that these are only highly chlorinated substances (i.e., decachlorobiphenyl, nonachlorobiphenyl, heptachlorobiphenyl), which have BCFs in the 10⁵ range noting that octachloronaphthalene has a measured BCF of <1000 (Fox et al. 1994, Gobas et al. 1989, Oliver and Niimi 1988) and all have log K_ow values less than 9.0.  The log K_ow of the C₂₀ cyclo alkane fraction and >C₂₀ fractions is ~9.0 or greater than 9.0.  At this log K_ow there are no empirically observed BCF (laboratory) or BAF values recorded for any species of invertebrates or vertebrates.  This is most likely a result of very low bioavailability (and thus poor dietary assimilation efficiency). Therefore the predicted BCF and BAF values for the >C₂₀ fraction are considered to be out of the parametric domain of the Arnot-Gobas model (2003) and considered as being highly uncertain and not reliable values. The bioaccumulation potential of the >C₂₀ fraction is thus expected to be very low which means the BCFs and BAFs for these fractions is also very likely < 5000.

Based on reported data, aquatic organisms readily take up petroleum hydrocarbons, primarily into lipids. Moderate concentrations can be found in some muscle and internal organs of fish based on chronic concentration of petroleum hydrocarbons and the distribution of fatty tissues. When fish are no longer exposed to these substances, depuration occurs quickly. Observed reductions in tissue burdens of hydrocarbons with increasing exposure time indicate biotransformation in fish. The tendency for specific types of petroleum hydrocarbons (PHC) to bioaccumulate in tissues suggests that these compounds could be transferred at low concentrations into the food chain, although they do not bioaccumulate to high levels or biomagnify in food chains. This pattern of uptake and depuration also indicates that pulsed exposures likely would not result in bioaccumulation over the long term.

Based on the combined evidence of empirical and modeled BCFs and BAFs, the HFOs assessed in this report contain large proportions of components that are highly bioaccumulative based on criteria in the Persistence and Bioaccumulation Regulations (Canada 2000).

No components of these HFOs were found to be both persistent and bioaccumulative based on criteria in the Persistence and Bioaccumulation Regulations.

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Potential to Cause Ecological Harm

Ecological Effects Assessment

Limited experimental aquatic toxicity data were obtained for several of the HFO CAS RNs considered here (EMBSI 2008a, b, c).

The experimental toxicity data for CAS RN 64741-80-6 (Table A3.8 in Appendix 3) indicate that at moderate concentrations, this HFO does not have a harmful effect on rainbow trout, green algae or water flea. However, the HFO tested was a relatively heavy fraction and therefore did not contain many of the C₁₅ to C₂₀ hydrocarbons that would likely contribute to aquatic toxicity.

CONservation of Clean Air and Water in Europe (CONCAWE) developed an aquatic toxicity model specific to petroleum hydrocarbon mixtures called PetroTox (2009). PetroTox assumes toxicological action via narcosis and therefore accounts for additive effects according to the toxic unit approach (PetroTox 2009). It models the toxicity of petroleum hydrocarbons dissolved in the water fraction for C₅-C₄₁ compounds; compounds smaller than C₅ are considered by the model to be too volatile to remain in water long enough to impart any significant aquatic toxicity, and compounds greater than C₄₁ are assumed too hydrophobic and immobile to impart any toxicity. PetroTox generates estimates of toxicity with a median lethal loading concentration (LL₅₀) rather than a median lethal concentration (LC₅₀) due to the insolubility of petroleum substances in water. The LL₅₀ value is the amount of petroleum substances needed to generate a water-accommodated fraction (WAF) that is toxic to 50% of the test organisms. It is not a measure of the concentration of the petroleum components in the WAF.

A range of aquatic toxicity predictions were obtained using the PetroTox (2009) model (Table A3.9 in Appendix 3). These results indicate that all of these HFOs are potentially hazardous to many aquatic organisms (acute LL₅₀ ≤1.0 mg/L), although some CAS RNs are not hazardous to some marine organisms. The estimated toxicity values are much lower than the experimental data from EMBSI (2008a, b, c). PetroTox (2009) estimates that the bulk of the toxicity of these CAS RNs is due to the C₁₅-C₂₅ di- and polyaromatic fractions; those CAS RNs that are not hazardous to some marine organisms tend to have higher boiling-point ranges.

To determine whether the PetroTox modelled data are appropriate, a read-across approach was used to compare HFO-modelled toxicity to Fuel Oil No. 6 (Bunker C fuel oil) toxicity. Fuel Oil No. 6 is a dense viscous oil with a wide boiling-point range of 160–700ºC (Environment Canada 2010). Table A3.10 in Appendix 3 presents Fuel Oil No. 6 acute toxicity data to aquatic organisms.

Aquatic LC₅₀ values for Fuel Oil No. 6 range from 0.9 to 4.6 mg/L. These values fall within the range of 0.1 to 18.6 mg/L for many of the modelled LL₅₀s for HFOs from PetroTox (Table A3.10 in Appendix 3). Therefore, the modelled data are considered to reflect the toxicity of a similar, commercially available, heavy fuel oil. An average toxicity value to Rhepoxynius abronius of 0.1 mg/L is the lowest LL₅₀ generated by PetroTox under an acute exposure to a marine amphipod. This will be the critical toxicity value (CTV) for marine exposures because no other ecotoxicity data were identified.

Terrestrial Compartment

Acute toxicity tests were not identified for any of the CAS RNs considered in this report, but identified for other PSSA HFOs. In an acute oral study conducted in rats, clear indications of intoxication were evident up to 24 hours post-treatment after a single dose of 2000 milligram/kilogram-body weight (mg/kg-bw) of CAS RN 64742-90-1 (steam-cracked residue) (ECB 2000b). An oral LD₅₀ of 5500 mg/kg-bw was established (after 14 days of observation) in rats after a single oral exposure to Fuel Oil No. 6 (Bunker C oils from various European manufacturers). Total (100%) mortality was observed at 10 000 and 25 000 mg/kg-bw in the same study (ECB 2000b). Catalytically cracked clarified oil (CAS RN 64741-62-4) exhibited an oral LD₅₀ of 4320 mg/kg-bw (after 14 days of observation) after a single exposure to rats. A dermal LD₅₀ of >3 160 mg/kg-bw in rabbits for CAS RN 64742-90-1 was identified (ECB 2000a).

Ecological Exposure Assessment

The subset of HFOs considered in this report have been identified as site-restricted, indicating that they are not expected to be transported off or released from refinery or upgrader facility sites. Release to the ecosystem is therefore expected to be negligible and exposure is not expected.

Characterization of Ecological Risk

All of these HFOs contain high proportions of components (mostly ≥C₃₀) that are persistent based on criteria in the Persistence and Bioaccumulation Regulations (Canada 2000).

Based on the combined evidence of empirical and modeled data on bioconcentration and/or bioaccumulation, the HFOs assessed in this report likely contain a large proportion of C₁₅-C₂₀ components that are highly bioaccumulative based on criteria in the Persistence and Bioaccumulation Regulations (Canada 2000).

No components of these HFOs were found to be both persistent and bioaccumulative based on criteria in the Persistence and Bioaccumulation Regulations.

Based on information obtained from a variety of sources (voluntary industry submissions, an in-depth literature review, and a search of material safety data sheets), the HFOs considered in this screening assessment have been identified as site-restricted - i.e., they are not expected to be transported off refinery or upgrader facility sites. These HFOs are consumed on-site or are blended into other substances leaving the site under different CAS RNs. Measures (including provincial/territorial operating permit requirements, and best practices and guidelines put in place by the petroleum industry) are in place to minimize releases from refineries and upgrader facilities. As a result of these factors, the likelihood of exposure, and potential for risk, of organisms in the environment to HFOs under these CAS RNs is considered to be low.

Uncertainties in Evaluation of Ecological Risk

The site-restricted HFOs are UVCBs and therefore their specific chemical compositions are not well defined. HFO streams under the same CAS RN can vary significantly in the number, identity and proportion of constituent compounds, depending on operating conditions, feedstocks and processing units.

All modelling of a substance’s physical and chemical properties and persistence, bioaccumulation and toxicity characteristics is based on chemical structures. Since these substances are UVCBs, they cannot be represented by a single, discrete chemical structure. Therefore, for the purposes of modelling, representative structures that would provide conservative estimates were identified. Given that more than one representative structure may be derived for the same UVCB, it is recognized that structure-related uncertainties exist for these substances. The physical-chemical properties of 30 representative structures were used to estimate the overall behaviour of the HFOs. The reliance on this method generates additional uncertainties in persistence and bioaccumulation predictions. CAS RN 68476-32-4 did not have an identified carbon range or boiling-point range. As such, it was assumed to behave in a similar fashion to the other site-restricted HFOs identified in this report. However, a lack of information on this CAS RN adds considerable uncertainty if its chemical structures differ significantly from that of the other HFOs in this assessment.

As these substances are classified as site-restricted, environmental releases and exposures are expected to be negligible. However, monitoring data for specific CAS RN were not identified to verify this assumption.

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Potential to Cause Harm to Human Health

Health Effects Assessment

There are only a limited number of studies evaluating the health effects of site-restricted HFOs available. Therefore, in order to characterize the toxicity of these substances, additional HFOs in the PSSA-- similar from both a process and physical-chemical perspective--were evaluated for their toxicological effects. Since both the site-restricted and the additional PSSA high priority HFO substances have similar physical-chemical and toxicological properties, the toxicological data were pooled across CAS RNs to construct a toxicological profile representative of all HFOs. This approach was taken in order to represent the toxicity of HFOs as a group. Appendix 4 contains a summary of available information on health effects for site-restricted HFO substances and the lowest-observed-adverse-effect-levels/concentrations (LOAELs/LOAECs) observed from the pooled toxicological data.

The HFO category of petroleum mixtures represented in Appendix 4 includes both residual fuels from distillation or cracking units and blended products, and consists of aromatic, aliphatic and cycloalkane hydrocarbons; heavy fuels may also contain hydrogen sulphide.

The acute toxicity of HFOs generally appears to be low. Oral median lethal dose (LD₅₀) values were found to range from >2000 to >25 000 mg/kg-bw in rats. Dermal LD₅₀ values ranged from >2000 to >5350 mg/kg-bw in rabbits and >2000 mg/kg-bw in rats. One inhalation study noted a median lethal concentration (LC₅₀) value of >3700 mg/m³ in rats (CONCAWE 1998; ECB 2000a; API 2004; US EPA 2005). Minimal to moderate skin irritation was observed in all cases of acute dermal exposure. Available data indicate that the HFOs or components tested are generally minimally irritating to the eye (CONCAWE 1998).

Short-term and subchronic dermal toxicity studies conducted over periods of 3 days to 13 weeks are available for HFO substances. Minimal to severe skin irritation was observed in all rat studies; the lowest dose examined for skin irritation was 8 mg/kg-bw per day (Mobil 1994a, b). Selected systemic effects observed in these studies include: mortality, reduced body weight gain and body weight, changes in specific organ weights (i.e., liver and thymus), reduced haematology parameters (e.g., haemoglobin, erythrocytes and platelets) and aberrant serum chemistry (UBTL 1990, 1994; API 1983; Mobil 1988, 1990, 1992, 1994a, b; Feuston et al. 1994, 1997). For short-term exposure, a LOAEL of 1 mg/kg-bw per day was determined for maternal toxicity following dermal exposure of pregnant CD rats to catalytically cracked clarified oil (CAS RN 64741-62-4) at doses of 0.05, 1.0, 10, 50 or 250 mg/kg-bw per day from gestational days 0 to 19. Effects noted at the LOAEL include: significantly decreased maternal body weight, decreased body weight gain and feed consumption, as well as decreased gravid uterine weight and the occurrence of red vaginal exudates (Hoberman et al. 1995). For subchronic exposure, a LOAEL of 8 mg/kg-bw per day was established following dermal exposure of male and female rats to CAS RNs 64741-62-4 or 64741-81-7 at doses of 8, 30, 125, 500 or 2000 mg/kg-bw per day for 13 weeks. Effects noted at the LOAEL include: decreased platelet counts and increased liver weight, as well as dose-related skin irritation (Feuston et al. 1994, 1997; Mobil 1988, 1992, 1994b).

One short-term inhalation study was conducted using CAS RN 64742-90-1. A LOAEC of 540 mg/m³ for decreased body weight and increased liver weight was observed in Fisher 344 rats following administration of 540 or 2000 mg/m³, 6 hours per day for 9 days (Gordon 1983).

In a short-term oral toxicity study conducted for CAS RN 64741-62-4, a single dose of 2000 mg/kg or single doses of 125, 500 or 2000 mg/kg were administered to pregnant Sprague-Dawley rats on one of gestational days 11–15 or on gestational day 12, respectively. Decreased maternal body weight gain and thymus weights were reported, regardless of treatment day, for the gestational-day segment of the study. Dose-related decreased maternal body weight gain and thymus weights were reported for the dose-response segment of the study (Feuston and Mackerer 1996). There were no subchronic or chronic oral toxicity studies available in the HFO literature.

The genotoxicity of HFOs has been evaluated with in vivo and in vitro assays. Results of in vivo genotoxicity testing with HFO substances were mixed; three HFO substances were assessed. Positive results were observed for micronuclei induction, unscheduled deoxyribonucleic acid (DNA) synthesis (UDS) and sister chromatid exchange assays conducted in rats and mice (Khan and Goode 1984; API 1985a, b). Negative results were observed for micronuclei induction and bone marrow chromosomal aberrations in two studies assessing a heavy-vacuum gas oil and a catalytically cracked clarified oil, respectively, in rats (API 1985c; Mobil 1987a).

In vitro assays evaluating the genotoxicity of HFOs also produced mixed results. Positive results were obtained in the Ames, modified Ames and mouse lymphoma assays, as well as for unscheduled DNA synthesis and cell transformation (API 1985c, d, 1986a; Blackburn et al. 1984, 1986; Mobil 1985; Feuston et al. 1994, Brecher and Goode 1983, 1984). Regarding Fuel Oil No. 6, negative results were obtained in the mouse lymphoma and Ames assays (for forward and reverse mutations), as well as for sister chromatid exchange. Negative results for other HFOs were limited and observed only in one forward mutation assay and one cell-aberration assay (Farrow et al. 1983; API 1985e; Vandermeulen et al. 1985; Vandermeulen and Lee 1986; Mobil 1987b). Equivocal results were observed in a mouse embryo transformation assay, in a forward mutation assay and in one sister chromatid exchange assay (Papciak and Goode 1984; API 1985f, 1986b). The overall genotoxicity database indicates that while the results varied depending on the substance tested and the assay used, HFOs display genotoxic potential.

HFOs have been classified by the European Commission as Category 2 carcinogens (may cause cancer) (European Commission 1994; ESIS 2008) and by the International Agency for Research on Cancer (IARC) as Group 2B carcinogens (possibly carcinogenic to humans) for residual (heavy) fuel oils (IARC 1989a).

A number of skin painting studies were conducted in mice, rabbits and monkeys to investigate the dermal carcinogenic potential of HFOs using both chronic and initiation/promotion methodologies. Skin tumours, including both malignant carcinomas and benign papillomas, were observed in all studies (Smith et al. 1951; Shapiro and Getmanets 1962; Getmanets 1967; Shubik and Saffiotti 1955; Saffiotti and Shubik 1963; API 1989a, b; McKee et al. 1990; Blackburn et al. 1984, 1986; Bingham and Barkley 1979; Bingham et al. 1980; Lewis 1983; Weil and Condra 1977; Sun Petroleum Products Co. 1979). Exposure durations for the chronic studies ranged from 25 weeks to the animals’ lifetimes, with reported tumour latency periods ranging from 8 to 113 weeks. In several studies, however, the durations of exposures and latencies were not specified (IARC 1984, 1989a, b; CONCAWE 1998). In a chronic study, male mice were dermally treated with CAS RN 64741-62-4 at doses of 8.4, 16.8, 42, 83.8 or 167.6 mg/kg-bw, three times per week for a lifetime. Significant skin tumour formation was observed at all doses in a dose-response fashion (McKee et al. 1990). In the one initiation study that was identified, male mice were dermally treated with CAS RN 64741-62-4 at a dose of 16.8 mg/kg-bw for five consecutive days. Significant skin tumour formation was observed at this dose. In the corresponding promotion study, no increase in histologically confirmed tumour incidence was observed. A statistically significant increase in the number of mice with gross masses (and shortened latency periods) was observed, however, indicating possible weak promoting activity (API 1989a).

Regarding tumorigenicity of HFOs, it is recognized that they may contain appreciable concentrations of minor constituents such as PAHs, and the quantity of this fraction can vary depending on the nature and amount of diluent fractions and whether the residue component is cracked or uncracked. The Government of Canada has completed a human health risk assessment of five PAHs, consisting of a critical review of relevant data under the Priority Substances Program. Based primarily on the results of carcinogenicity bioassays in animal models, these PAHs were classified as “probably carcinogenic to humans:” substances for which there is believed to be some chance of adverse effects at any level of exposure (Environment Canada 1994). Further assessment of minor constituents is beyond the scope of the current assessment.

HFOs have also been investigated for their reproductive and developmental effects. A LOAEL of 1.0 mg/kg-bw per day was identified for reproductive and developmental toxicity after dermal exposure of pregnant rat dams to catalytically cracked clarified oil (CAS RN 64741-62-4) during gestational days 0 to 19 (the no-observed-adverse-effect-level (NOAEL) was 0.05 mg/kg-bw per day). Reproductive effects included decreased number of live foetuses and increased incidences of resorptions, early resorptions and percent of dead or resorbed conceptuses per litter. Foetal developmental variations were also observed in this study but were determined not to be treatment-related (Hoberman et al. 1995). In another short-term dermal study, a LOAEL of 8 mg/kg-bw per day was established for treatment-related developmental toxicity after exposing pregnant Sprague-Dawley rats to CAS RN 64741-62-4 during gestation (Feuston et al. 1989; Mobil 1987c). Developmental effects included a low incidence of foetal external abnormalities including cleft palate, micrognathia (shortened lower jaw) and kinked tail.

Only one oral reproductive and developmental study was identified for any HFO substance. A LOAEL of ≥125 mg/kg was established based on a dose-related increase in resorptions (concomitant decrease in litter size), decreased foetal body weight and increased incidences of skeletal malformations in this acute study that exposed pregnant Sprague-Dawley rats to CAS RN 64741-62-4 during gestation (Feuston and Mackerer 1996). No reproductive or developmental toxicity studies were identified for any HFO substance via the inhalation route of exposure.

Although results varied depending on the substance tested, the overall weight-of-evidence suggests that HFOs exhibit reproductive and developmental toxicity in laboratory animals.

Epidemiological data were not available for consideration in the human health effects evaluation of HFO substances.

Characterization of Risks to Human Health

Site-restricted HFOs were identified as a high priority for action because they were considered to present a high hazard to human health. A critical effect for the initial categorization of site-restricted HFO substances was carcinogenicity, based primarily on the classifications of HFOs by international agencies. These substances are classified by the European Commission as Category 2 carcinogens (European Commission 1994; ESIS 2008) and by IARC as Group 2B carcinogens (IARC 1989a). However, the HFOs considered in this report have been identified as site-restricted (i.e., indicating that they are not expected to be transported off refinery or upgrader facility sites), and therefore general population exposure is expected to be negligible. Accordingly, the likelihood of exposure to Canadians is considered to be low; hence, the risk to human health is likewise considered to be low.

Uncertainties in Evaluation of Human Health Risk

The site-restricted HFOs are considered to be UVCBs and their specific chemical compositions are not well defined. HFO streams under the same CAS RN can vary significantly in the number, identity and proportion of constituent compounds, depending on operating conditions, feedstocks and processing units. Consequently, it is difficult to obtain a truly representative toxicological data set for individual CAS RNs. For this reason all available toxicological data for substances with similar petroleum processing and physical-chemical properties were pooled across multiple CAS RNs to develop a comprehensive toxicity profile by including the available data for all HFOs. Specific physical-chemical properties of some HFOs were not available, therefore, properties of representative HFOs were used as needed.

The scope of this screening assessment does not involve full investigation of the mode of induction of effects.

The PSSA screening assessments evaluate substances that are complex mixtures (UVCBs) composed of a number of substances in various proportions due to the source of the crude oil and its subsequent processing. Monitoring information or provincial release limits from petroleum facilities target broad releases such as oils and greases to water or air. These widely encompassing release categories do not allow for detection of individual complex mixtures or production streams. As such, the monitoring of broad releases cannot provide sufficient data to associate a detected release with a specific substance identified by a CAS RN, nor can the proportion of releases attributed to individual CAS RNs be defined.

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Conclusion

All of the HFOs considered in this assessment may be comprised of significant proportions of components (mostly ≥C₃₀) that persist in soil, water and sediments based on criteria in the Persistence and Bioaccumulation Regulations (Canada 2000).

Based on the combined evidence of empirical and modeled bioconcentration/ bioaccumulation potential, the HFOs assessed in this report likely contain a large proportion of C₁₅-C₂₀ components that are highly bioaccumulative based on criteria in the Persistence and Bioaccumulation Regulations.

No components of these HFOs were found to be both persistent and bioaccumulative based on criteria in the Persistence and Bioaccumulation Regulations.

Based on the information presented in this screening assessment, the basis for categorization for human health hazard was carcinogenicity. HFOs also exhibit properties of genetic toxicity and appear to adversely affect reproduction and development.

The HFOs listed in this screening assessment (CAS RNs 64741-45-3, 64741-61-3, 64741-80-6, 68333-22-2, 68333-27-7, 68476-32-4 and 68478-17-1) are restricted to petroleum refineries and upgrader facilities; therefore, exposure of the general population and the environment is not expected. It is concluded that these site-restricted HFOs are not entering the environment in a quantity or concentration or under conditions that have or may have an immediate or long-term harmful effect on the environment or its biological diversity; that constitute or may constitute a danger to the environment on which life depends; or that constitute or may constitute a danger in Canada to human life or health.

It is therefore concluded that these site-restricted HFOs do not meet any of the criteria set out in section 64 of CEPA 1999.

Because these substances are listed on the Domestic Substances List, their import and manufacture in Canada are not subject to notification under subsection 81(1) of CEPA 1999. Given the potential hazardous properties of these substances, there is concern that new activities that have not been identified or assessed could lead to these substances meeting the criteria set out in section 64 of the Act. Therefore, application of the Significant New Activity provisions of the Act to these substances is being considered, so that any proposed new manufacture, import or use of these substances outside a petroleum refinery or upgrader facility is subject to further assessment, to determine if the new activity requires further risk management consideration.

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Appendix 1: Description of the Nine Groups of Petroleum Substances

Table A1.1: Description of the nine groups of petroleum substances

^[1] These groupings were based on classifications developed by CONCAWE and a contractor’s report presented to the Canadian Petroleum Products Institute (CPPI) (Simpson 2005).

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Appendix 2: Engineering Process Flow Diagrams for Heavy Fuel Oils ^[4]

(Please see the PDF version to get better image quality)

Figure A2.1. Process flow diagram for CAS RN 64741-45-3 in a refinery (Hopkinson 2008)

CAS RN 64741-45-3 is a processing intermediate formed after atmospheric distillation of crude oil in a refinery.

Figure A2.2. Process flow diagram for CAS RN 64741-61-3 in a refinery (Hopkinson 2008)

CAS RN 64741-61-3 is a processing intermediate formed after catalytic cracking in an upgrader.

Figure A2.3. Process flow diagram for CAS RN 64741-80-6 in a refinery (Hopkinson 2008)

CAS RN 64741-80-6 is shown to be a processing intermediate formed after visbreaking in a refinery.

Figure A2.4. Process flow diagram for CAS RN 68333-22-2 in a refinery (Hopkinson 2008)

CAS RN 68333-22-2 is shown to be a processing intermediate formed after atmospheric distillation in a refinery.

Figure A2.5. Process flow diagram for CAS RN 68333-27-7 in a refinery (Hopkinson 2008)

CAS RN 68333-27-7 is a processing intermediate shown to be formed after hydrotreating in a refinery.

Figure A2.6. Process flow diagram for CAS RN 68476-32-4 in a refinery (Hopkinson 2008)

CAS RN 68476-32-4 is a processing intermediate shown to be formed after atmospheric distillation in a refinery.

Figure A2.7a. Process flow diagram for CAS RN 68478-17-1 in a refinery (Hopkinson 2008)

CAS RN 68478-17-1 is a processing intermediate shown to be formed after vacuum distillation in a refinery.

Figure A2.7b. Process flow diagram for CAS RN 68478-17-1 in an upgrader (Hopkinson 2008)

CAS RN 68478-17-1 is a processing intermediate shown to be formed after coking in an upgrader.

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Appendix 3: Data Tables for Site-restricted HFOs

Table A3.1a. Substance identity for site-restricted HFOs

Abbreviations: CAS RN, Chemical Abstracts Service Registry Number; DSL, Domestic Substances List; wt, weight.
^[1]All DSL names were identical to those in NCI (2006).

Table A3.1b. Physical and chemical properties for representative structures of HFOs^[a]

^[a] All values are modelled unless denoted with an (e) for experimental data.
^[b] This is the maximum vapour pressure of the surrogate; the actual vapour pressure as a component of a mixture will be lower due to Raoult’s Law (the total vapour pressure of an ideal mixture is proportional to the sum of the vapour pressures of the mole fractions of each individual component). The lightest C₉ and heaviest C₅₀ representative structures were chosen to estimate a range of vapour pressures from the minimum to maximum values.
^[c] Estimated sub-cooled liquid vapour pressures were obtained from AEROWIN (Version 1.01) in EPIsuite (2008). Sub-cooled liquid vapour pressures were only estimated for components determined to be solid at 25°C (i.e., ≥C₂₀).

Table A3.1b cont. Physical and chemical properties for representative structures of HFOs^[a]

^[a] All values are modelled unless denoted with an (e) for experimental data.
^[d] Henry’s Law constants for C₂₀–C₃₀ representative structures were calculated with HENRYWIN Version 3.10 from EPIsuite (2008), using both sub-cooled liquid solubility and sub-cooled liquid vapour pressure. Henry’s Law constants for C₅₀ representative structures were not calculated as sub-cooled liquid solubility data were not available. Solubility data gave anomalously high values for substances that have negligible solubility and volatility.
^[e] Maximum water solubility was estimated for each surrogate based on its individual physical-chemical properties. The actual water solubility of a component in a mixture will be lower, as the total water solubility of an ideal mixture (Table 2 in text) is proportional to the sum of the water solubilities of the mole fractions of each individual component (Banerjee 1984).
^[f] Estimated sub-cooled liquid solubilities were obtained from the CONCAWE1462 database within PetroTox (2009). The estimates contained within the database were calculated using the SPARC Performs Automated Reasoning in Chemistry (SPARC 2009). Sub-cooled liquid solubility values were only estimated for components determined to be solid at 25°C (i.e., ≥C₂₀). Sub-cooled liquid solubility data were not available for the C₅₀ components.

Table A3.2. Boiling point ranges for HFOs

Table A3.3. Representative structures that would be included for each CAS RN^[*]

^[*] No information was found on the boiling point or carbon range of CAS RN 68476-32-4 and therefore it is unclear what structures would be representative.

Table A3.4. Modelled data for primary (BioHCwin 2008) and ultimate (BIOWIN 2008) biodegradation of representative structures of HFOs in water

^[1] Half-life estimations are for water.

Table A3.5. Potential presence of representative structures likely to be persistent in water, soil, and sediment^[1]

^[1] CAS RN 68476-32-4 is not included due to a lack of data on its boiling point.

Table A3.6. Fish BAF and BCF predictions for representative structures of HFOs using BCFBAF (2009) with metabolism

^[a] Biotransformation rate constant for 10 g fish.
^[b] Representative structures that were remodelled using BAF-QSAR v1.5 based on similar structures with experimental data.
^[*] Any representative structures with estimated log Kow values > 8 were excluded from this analysis due to model limitations.
(e): Experimental data.
^[1] EpiSuite 2008.
^[2] Arnot and Gobas 2003.

Table A3.7. Comparisons of experimental BCFs and modeled BCFs (BCFBAF 2008) on some representative structures of HFOs.

^[a] Experimental BCFs from various sources.
^[b] Modeled BCFs using BCFBAF (2008); BCF of a lower trophic fish were chosen to match the lipid content of fish in the Japanese database.
^[c] C₁₃ 2-iso-Propylnaphthalene: The only measured BCF found >5000 out of the thirty-one data points; it is greater than the modeled value by an order of magnitude.

Table A3.8. Empirical data for aquatic toxicity of CAS RN 64741-80-6 (EMBSI 2008a, b, c)

EL₅₀: The loading concentration of a substance that is estimated to cause some toxic sublethal effect on 50% of test organisms.
LL₅₀: The loading concentration of a substance that is estimated to be lethal to 50% of test organisms.

Table A3.9. Modelled acute LL₅₀ (mg/L) data for aquatic toxicity (PetroTox 2009)

Table A3.10. Aquatic toxicity of Fuel Oil No. 6 (Bunker C)

Table A3.11. Atmospheric degradation of representative structures via reaction with hydroxyl radicals (AOPWin 2008).

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Appendix 4: Summary of Health Effects Information from Pooled Toxicological Data for HFO Substances

^[1] Site-restricted HFO substances are indicated in bold.
^[2] Abbreviations: LC₅₀, median lethal concentration; LD₅₀, median lethal dose; LOAEC, lowest-observed-adverse-effect concentration; LOAEL, lowest-observed-adverse-effect level; NOAEC, no-observed-adverse-effect concentration.
^[3] The following formula was used for conversion of provided values into mg/kg-bw: x ml/kg-bw × ρ.
^[4] Body weight (bw) not provided, thus laboratory standards from Salem and Katz, Inhalation Toxicology, 2006 were used.
^[5] Effective number = number of mice given adequate exposure minus number that died without a tumour (IARC 1989b).
^[6] The following formula was used for conversion of provided values into mg/kg-bw: (% of dilution x x mL x ρ)/bw.
^[7] Density not provided, thus a density from CONCAWE 1998 was used.
^[8] A volume/volume dilution was assumed.

Footnotes

^[1] A determination of whether one or more of the criteria of section 64 are met is based upon an assessment of potential risks to the environment and/or to human health associated with exposures in the general environment. For humans, this includes, but is not limited to, exposures from ambient and indoor air, drinking water, foodstuffs, and the use of consumer products. A conclusion under CEPA 1999 on the petroleum substances in the Chemicals Management Plan (CMP) is not relevant to, nor does it preclude, an assessment against the hazard criteria specified in the Controlled Products Regulations, which is part of the regulatory framework for the Workplace Hazardous Materials Information System (WHMIS) for products intended for workplace use. Similarly, a conclusion based on the criteria contained in section 64 of CEPA 1999 does not preclude actions being undertaken in other sections of CEPA 1999 or other Acts.
^[2] For the purposes of the screening assessment of PSSA substances, a site is defined as the boundaries of the property where a facility is located. In these cases, facilities are either petroleum refineries or upgraders.
^[3] For the purposes of the screening assessment of PSSA substances, a closed system is defined as a system within a facility which does not have any releases to the environment, and in which losses are collected and either recirculated or destroyed.
^[4] Red dotted line indicates the process relevant to the particular CAS RN; FCCU: Fluid Catalytic Cracking Unit; LPG: Liquified Petroleum Gas.