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Substance Profile for The Challenge
(1,1,4,4-tetramethyl-1,4-butanediyl)bis[(1,1-dimethylethyl)peroxide] CAS No. 78-63-7

Introduction

The Canadian Environmental Protection Act, 1999 (CEPA 1999) required the Minister of Health and Minister of the Environment to categorize the approximately 23 000 substances on the Domestic Substances List (DSL). Categorization involved identifying those substances on the DSL that are a) considered to be persistent (P) and/or bioaccumulative (B), based on criteria set out in the Persistence and Bioaccumulation Regulations (Government of Canada, 2000), and “inherently toxic” (iT) to humans or other organisms, or b) that present, to individuals in Canada, the greatest potential for exposure (GPE).

Further to this activity, the Act requires the Minister of the Environment and the Minister of Health to conduct screening assessments of substances that meet the categorization criteria. A screening assessment involves a scientific evaluation of available information for a substance to determine whether the substance meets the criteria set out in section 64 of CEPA 1999. Based on the results of a screening assessment, the Ministers can propose taking no further action with respect to the substance, adding the substance to the Priority Substances List (PSL) for further assessment or recommending the addition of the substance to the List of Toxic Substances in Schedule 1 of CEPA 1999 and, where applicable, the implementation of virtual elimination of releases to the environment.

A number of substances have been identified by the Ministers as high priorities for action based on the information obtained through the categorization process. This includes substances:

  • that were found to meet all of the ecological categorization criteria, including persistence, bioaccumulation potential and inherent toxicity to aquatic organisms (PBiT), and that are known to be in commerce in Canada, and/or
  • that were found either to meet the categorization criteria for GPE or to present an intermediate potential for exposure (IPE), and were identified as posing a high hazard to human health based on available evidence on carcinogenicity, mutagenicity, developmental toxicity or reproductive toxicity.

Based on a consideration of the ecological and/or human health concerns associated with these substances, and the requirement under section 76.1 of CEPA 1999 for the Ministers to apply a weight of evidence approach and the precautionary principle when conducting and interpreting the results of an assessment, sufficient data are currently available to consider these substances as meeting the criteria under Section 64 of CEPA 1999.

As such, the Ministers have issued a Challenge to industry and other interested stakeholders through publication in Canada Gazette Part I December 9, 2006 to submit, within the timelines stated in the Challenge section of this document, below, specific information that may be used to develop and benchmark best practices for risk management and product stewardship.

The substance (1,1,4,4-tetramethyl-1,4-butanediyl)bis[(1,1-dimethylethyl)peroxide] was identified as a high priority for action as it was found to be persistent, bioaccumulative and inherently toxic to aquatic organisms and is believed to be in commerce in Canada. The technical human health and ecological information, that formed the basis for concern associated with this substance, is contained in Appendices I and II, respectively.

Substance Identity

For the purposes of this report, this substance will be referred to as DMHBP, which has been derived from the inventory name 2,5-Dimethylhexane-2,5-di-tert-butylperoxide.

CAS Registry Number 78-63-7
Inventory names Peroxide, (1,1,4,4-tetramethyl-1,4-butanediyl)bis[(1,1-dimethylethyl); di-tert-butyl 1,1,4,4-tetramethyltetramethylene diperoxide; 2,5-Dimethyl-2,5-di (t-butylperoxy) hexane; 2,5-Dimethylhexane-2,5-di-tert-butylperoxide
Other names (1,1,4,4-Tetramethyltetramethylene)bis(tert-butyl peroxide); 2,5-Bis(tert-butyldioxy)-2,5-dimethylhexane; 2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane; Interox DHBP, DHBP 451C/G; Kayahexa AD, AD 40, AD 40C; Luperco 101X45, 101XL; Luperox 101, 101XL, 101XL45; Lupersol 101, 101XL, L 101;Perhexa 2.5B, 2.5B40, 25B, 25B40; Trigonox 101, 101-40D, 101-40MD-GR, 101-50, 101E10, 101E5, XQ8; Varox 50, DBPH, DBPH 50, Liquid
Chemical group Discrete organics
Chemical sub-group Dialkyl Peroxide
Chemical formula C16H34O4
Chemical structure Image of Chemical Structure
SMILES O(OC(C)(C)C)C(CCC(OOC(C)(C)C)(C)C)(C)C
Molecular mass 290.45 g/mol

Based on information submitted in response to a legal Notice published in 2006 under section 71 of CEPA 1999, DMHBP was not manufactured in Canada in 2005 in a quantity meeting the 100 kg reporting thresholds. Ten companies reported importing up to 100,000 kg into Canada in 2005 for activities described as plastics product manufacturing, basic chemical manufacturing, rubber product manufacturing (which could include tires, hoses and other rubber products), resin, synthetic rubber, and artificial synthetic fibers and filaments manufacturing and the wholesale trade/distribution of chemical (except agricultural) and allied products. DMHBP can be used in polymer processing as an initiator for crosslinking of polyolefins. It may be used as a polymerisation initiator for plastics and in rubber processing for the production of window seals and automotive seals, hoses, and soles of shoes. It may also be used for the curing of some resins for applications ranging from boat hulls and swimming pools to bodywork parts.

THE CHALLENGE

Based on the information presented in Appendix II of this document, it is expected that the screening assessment of this substance will conclude that it satisfies the definition of toxic under section 64 of CEPA 1999 in that it “may enter 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”. The substance will then be proposed for addition to the List of Toxic Substances in Schedule I of the Act and proposed for virtual elimination of releases to the environment.

Subsequent risk management activities will be based on the objective of eliminating the release of a measurable quantity of a PBiT substance to the environment. In the absence of further information on existing handling practices for these substances, proposed actions would be based on realistic worst case assumptions. At this time, prohibition is being considering through regulations, of the manufacture, use, sale, offer for sale and import of this substance, except for those activities controlled under the Pest Control Products Act and/or the Food and Drugs Act.

Opportunity to Submit Information on P, B and iT Properties

Through the categorization exercise, available experimental aquatic toxicity information as well as experimental data on the potential for a substance to persist or bioaccumulate in the environment were collected prior to December 2005. Where acceptable experimental data were not available, Quantitative Structure Activity Relationships (QSARs) or read across data were used to fill the data gaps. Since the categorization outcome on P, B, and iT form the basis for prioritizing this substance for action, and experimental data are preferred, interested parties have an opportunity to provide relevant experimental study information on the persistence, bioaccumulation, and inherent toxicity to aquatic organisms for this substance.

Efforts should focus on providing data for the endpoints for which quality experimental data does not already exist, as demonstrated by the information summarized in Appendix II of this document. As submitted data will be evaluated for completeness and robustness, it is recommended that stakeholders follow the guidance for test protocols and alternative approaches for test data, as described in Section 8 of the “Guidelines for the Notification and Testing of New Substances: Chemicals & Polymers”.[1]

Responses to this part of the challenge for this substance should be received at the address provided below by June 5, 2007.

Section 71 Notice

Information needed for improved decision-making with regard to risk assessment and management of this substance is being gathered using section 71 of CEPA 1999. This notice applies to any person who reported pursuant to the Canadian Environmental Protection Act, 1999 section 71 Notice with Respect to Selected Substances Identified as Priority for Action, published in the Canada Gazette, Part I, on March 4, 2006.

The 2006 information mandated through the notice relates to, among other things, quantity of the substance imported, manufactured or used, types of uses of the substance, and releases of the substance to the environment.

Copies of the section 71 notice and guidance on how to comply with it are available from the Government of Canada Chemicals Portal (www.chemicalsubstanceschimiques.gc.ca/en/index.html), or from the contact provided below.

Responses to the section 71 notice must be received at the address provided below by June 5, 2007.

Opportunity to Submit Additional Information on Current Uses and Existing Control Measures to Inform the Risk Management Approach for this Substance

The Ministers of Health and Environment are inviting the submission of additional information that is deemed beneficial by interested stakeholders, relating to the extent and nature of the management/stewardship of substances listed under the Challenge.

Organizations that may be interested in submitting additional information in response to this invitation include those that manufacture, import, export or use this substance whether alone, in a mixture, in a product or in a manufactured item.

Additional information is being invited in the following areas:

  • Import, manufacture and use quantities
  • Substance and product use details
  • Releases to the environment and spill management
  • Current and potential risk management and product stewardship actions
  • Existing legislative or regulatory programs controlling/managing the substance
  • Information to support the development of a regulatory impact assessment.

A questionnaire is available which provides a detailed template as an example for the submission of this information. Guidance on how to respond to the challenge questionnaire is also available. Interested stakeholders are invited to provide available additional information, recognizing that not all questions in the questionnaire may be relevant to a particular substance, use, or industrial sector.

Copies of the questionnaire and associated guidance are available from the Government of Canada Chemicals Portal (www.chemicalsubstanceschimiques.gc.ca/en/index.html), or from the contact provided below.

Responses to this part of the challenge for this substance should be received at the address provided below by June 5, 2007.

Request for Documents and Submission of Information

Documents and instructions may be requested from the following contact. Information in response to the above Challenge must be submitted to this address.

DSL Surveys Coordinator
Place Vincent Massey, 20th Floor
351 Saint Joseph Boulevard
Gatineau QC K1A 0H3
Tel: 1-888-228-0530/819-956-9313
Fax: 1-800-410-4314 / 819-953-4936
Email: DSL.surveyco@ec.gc.ca

Appendix I
Human Health Information to Support The Challenge for
(1,1,4,4-tetramethyl-1,4-butanediyl)bis[(1,1-dimethylethyl)peroxide] (DMHBP) CAS No. 78-63-7

Introduction

Under the Canadian Environmental Protection Act, 1999 (CEPA, 1999), Health Canada undertook to categorize all substances on the Domestic Substances List (DSL) to identify those representing the greatest potential for human exposure (GPE) and those among a subset of substances considered persistant (P) and/or bioaccumulative (B) that are also considered to be “inherently toxic” to humans.

In order to efficiently identify substances that represent the highest priorities for screening assessment, Health Canada developed and applied a Simple Exposure Tool (SimET) to the DSL to identify those substances that meet the criteria for GPE, Intermediate Potential for Exposure (IPE) or Low Potential for Exposure (LPE), and a Simple Hazard Tool (SimHaz) to identify those substances that pose a high or low hazard.

DMHBP is considered to meet the criteria for LPE under SimET and does not meet the criteria for high hazard under SimHaz. This document summarizes the currently available information on which the SimET and SimHaz results are based.

Exposure Information from Health Related Components of DSL Categorization

As mentioned above, SimET was developed and used to identify substances on the DSL considered to represent GPE. This approach was based on three lines of evidence: 1) the quantity in commerce in Canada, 2) the number of companies involved in commercial activities in Canada (i.e., number of notifiers), and 3) the consideration by experts of the potential for human exposure based on various use codes. The proposed approach was released for public comment in November 2003 and also enabled designation of substances as presenting an IPE or LPE, based on criteria for quantity and nature of use (Health Canada, 2003).

Results of the Application of SimET

DMHBP has been determined to be LPE based on a consideration of the DSL nomination information listed below.

Nomination Information for DSL

Quantity in Commerce

The quantity reported to be manufactured, imported or in commerce in Canada during the calendar year 1986 was 10,000 kg.

Number of Notifiers

The number of notifiers for the calendar years 1984-1986 was less than 4.

Use Codes and Description

The following DSL use codes have been identified for the substance:

37 Polymer, crosslinking agent
76 Organic Chemicals, Industrial

Hazard Information from Health Related Components of DSL Categorization

Simple Hazard Tool (SimHaz)

SimHaz is a tool that has been used to identify, among all of the approximately 23 000 substances on the DSL, those considered to present either high or low hazard to human health based on formalized weight of evidence criteria and/or peer review/consensus of experts. This tool has been developed through extensive compilation of hazard classifications of Health Canada and other agencies and consideration of their robustness based on availability of transparent documentation of both process and criteria (Health Canada, 2005).

Results of the Application of SimHaz

DMHBP has not been classified for hazard by any of the agencies considered under the SimHaz tool and therefore does not meet the criteria for high hazard under SimHaz.

Uncertainties

SimET and SimHaz have been developed as robust tools for effectively identifying substances from the DSL considered to be human health related priorities for further consideration. It is recognized that they do not include a number of elements normally considered in a human health risk assessment such as a comprehensive characterization of exposure and hazard, a comparison of exposure metrics to hazard metrics and a detailed analysis of uncertainties.

References

Health Canada. 2003. Proposal for Priority Setting for Existing Substances on the Domestic Substances List under the Canadian Environmental Protection Act, 1999: Greatest Potential for Human Exposure.
http://www.hc-sc.gc.ca/ewh-semt/alt_formats/hecs-sesc/pdf/pubs/contaminants/existsub/exposure/greatest_potential_human_exposure-risque_exposition_humaine_e.pdf

Health Canada. 2005. Proposed Integrated Framework for the Health-Related Components of Categorization of the Domestic Substances List under CEPA 1999. http://www.hc-sc.gc.ca/ewh-semt/alt_formats/hecs-sesc/pdf/contaminants/existsub/framework-int-cadre_e.pdf

Appendix II
Ecological Information to Support The Challenge for
(1,1,4,4-tetramethyl-1,4-butanediyl)bis[(1,1-dimethylethyl)peroxide] (DMHBP)
CAS No. 78-63-7

Introduction

The information in this document will form the basis of a screening assessment under section 74 of CEPA, 1999. Data relevant to an ecological screening assessment were identified in original literature, review documents, commercial and government databases prior to December 2005. Properties and characteristics may also have been estimated using Quantitative Structure Activity Relationship (QSAR) models. In addition, an industry survey was conducted for the year 2005 through a Canada Gazette Notice issued pursuant to section 71 of CEPA 1999 (Environment Canada, 2006). This Notice requested data on the Canadian manufacture and import of the substance.

Physical and Chemical Properties

Table 1 contains experimental and modelled physical-chemical properties of DMHBP which are relevant to its environmental fate.

Table 1. Physical and chemical properties for DMHBP.

Property Type Value Temperature (°C) Reference
Boiling Point Experimental 42°C
Kirk-Othmer, 2001
Boiling Point Modelled 279.61°C
MPBPWIN v1.41
Melting Point Experimental 8°C
Kirk-Othmer, 2001
Melting Point Modelled 64.91°C
MPBPWIN v1.41
log Kow Modelled 6.55   25 Kowwin v.1.67
log Koc Modelled 5.21    PCKOCWIN v1.66
Vapour Pressure Experimental <0.01 kPa 20 Fisher Scientific MSDS, 2005
Vapour Pressure Modelled 0.56 Pa
MPBPWIN v1.41
Vapour Pressure Modelled 0.00422 mm Hg
MPBPWIN v1.41
Henry’s Law Constant Modelled 0.002575 
atm-m3/mole
25 HenryWin v3.10
Water solubility Modelled 0.035 mg/L 25 WSKOWWIN v1.41

Manufacture, Importation and Uses

Manufacture and Importation

Work was carried out under contract in 2002 by ChemInfo to determine the use of initiators in polymer resin manufacturing and processing in Canada. From this activity, it was determined that organic peroxide initiators were not manufactured in Canada in 2000 and approximately 300,000 kg of dialkyl peroxides were used in the Canadian polymer resin manufacturing process in 2000.

Under the CEPA section 71 Notice with respect to Selected Substances Identified as Priority for Action, Canadian companies who manufactured or imported (in 2005) greater than 100 kg of a substance listed in the notice were required to provide specific data regarding the substance to Environment Canada. Information gathered from this survey notice indicates that DMHBP was not manufactured in Canada in 2005 in a quantity meeting the 100kg reporting threshold.

In total, ten companies reported import of this substance, with three companies in the 100-1,000 kg/year range and seven companies in the 1,001 – 100,000 kg/year range. The importing companies identified their business activities as: plastics product manufacturing, basic chemical manufacturing, rubber product manufacturing (which could include tires, hoses and other rubber products), resin, synthetic rubber, and artificial synthetic fibers and filaments manufacturing and the wholesale trade/distribution of chemical (except agricultural) and allied products. In addition, six Canadian companies and one American company identified themselves as having a stakeholder interest in the substance.

Elsewhere, DMHBP has been identified as a US High Production Volume Chemical, with use reported under the Inventory Update Rule between 455 tonnes and 4545 tonnes from 1990 to 2002 (Sponsored by the Sponsor Society of the Plastics Industry Inc. (SPI) Organic Peroxide Producers Safety Division (OPPSD) 2001). DMHBP has also been identified as an OECD High Production Volume chemical. It is a European Union (EU) Low Production Volume Chemical, indicating that production within the EU has been estimated to be in the order of 10 tonnes per year. The database for Substances in Preparations in Nordic Countries indicates that in 2004, approximately 3 tonnes were in use in Sweden (SPIN database).

Uses

DMHBP is a dialkyl peroxide that may be used in polymer processing as an initiator for crosslinking of polyolefins and in the degradation of polypropylene. The carbon-carbon cross links provide rubber articles with the maximum resistance to heat, oxygen and compression set. It can be used as a polymerisation initiator for plastics and in rubber processing for the production of window seals and automotive seals, hoses, and soles of shoes. It may also be used for the curing of some resins for applications ranging from boat hulls and swimming pools to bodywork parts (Arkema). DMHBP may also be used as a vulcanizing agent or produced as a chemical intermediate.

Releases, Fate and Presence in the Environment

Releases

DMHBP is not naturally produced in the environment. Releases from anthropogenic sources have not been reported. However, due to the potentially explosive nature of peroxides when they dry, it is anticipated that waste material and container residues are commonly rinsed down the drain.

Fate

The high log Kow and Koc values indicate that this substance will likely partition to soil and sediments. Indeed, the results of the Level III Fugacity modelling indicates that if the chemical is released equally into the three major environmental compartments (air, water and soil), it will mainly partition into soil and sediments (Table 2), where the chemical has been indicated to persist (Table 3).

Table 2. Results of the Level III fugacity modelling (EPIWIN V3.12)


Fraction of Substance Partitioning to Each Medium (%)
Substance Released to: Air Water Soil Sediment
Air (100%) 52.8 0.583 13.9 32.7
Water (100%) 0.0535 1.75 0.0141 98.2
Soil (100%) 0.00144 0.00272 99.8 0.152
Air, water, soil (33.3% each) 0.197 0.94 46.1 52.8

A vapour pressure of 0.56Pa and Henry’s Law Constant of 2.6 x 10-3 atm-m3/mol indicate that DMHBP is relatively volatile. Therefore, if released solely to air, it should remain in this compartment. However the high Koc gives it a high affinity for particulate matter causing it to also partition to soil and sediment (~45%).

If released to water, DMHBP is expected to strongly sorb to suspended solids and sediment based on its extremely high log Koc value. Although volatilization from water surfaces may occur based on the Henry’s Law Constant, it is predicted that when released to water, the chemical partitions mainly to sediment.

If released to soil, DMHBP is expected to have extremely high adsorptivity to soil (i.e. expected to be immobile) based on an estimated Log Koc of ~5. DMHBP is expected to persist in soil (Table 3). The vapour pressure and Henry’s Law Constant indicate that volatilization may occur in dry and moist soil surfaces, however due to the extremely high adsorptivity to soil particles, volatilization is not expected to be significant. Therefore, if released to soil, DMHBP will remain in this compartment, which can be illustrated by the results of the Level III fugacity modelling (Table 2).

Presence in the Environment No monitoring data relating to the presence of this substance in environmental media (air, water, soil, sediment) have yet been identified.

Evaluation of P, B and iT Properties

Environmental Persistence

Once released in the environment, DMHBP appears to be relatively persistent in the environment, mainly in water, soil and sediments. Experimental persistence data is not available for air. It is expected to oxidize slowly, indicated by a predicted atmospheric oxidation half-life value of 2.377 days (EPIWIN v3.12). It is not expected to react with O3 or NO3. However, due to the weak oxygen-oxygen bond, almost all organic peroxides are thermally and photolytically sensitive. Di-tert butyl peroxide is structurally similar to DMHBP around the peroxide bond and absorbs light up to 340nm and has been found to photolyze to form tert-butoxy radicals at low temperatures (HSDB, 2006). It is expected that photolytic reactions will be the most important degradation process in the atmosphere for DMHBP resulting in rapid losses from air.

Table 3a. Modelled data for persistence

Medium Fate Process Endpoint Value Reference
Air Atm-oxidation Half life (days) 2.377 AOPWIN v1.91
Air Ozone reaction Half life (days) Non-reactive AOPWIN v1.91
Water/Soil Biodegradation Half life (days) 182 BIOWIN v4.02 (USM)
Water/Soil Biodegradation Probability 0.0388 BIOWIN v4.02
MITI Non-linear
Water/Soil Biodegradation Probability 0 TOPKAT

Table 3b. Empirical data for persistence

Medium Fate Process Endpoint Value (Range if applicable) Reference
Water Biodegradation % Biodegradation 4% NITE Database

The empirical biodegradation data (NITE database) shows 4% biodegradation over 28 days in a ready-biodegradation test as measured by GC analysis (Table 3b). This indicates that the half-life in water and soil is longer than 182 days (6 months).

For estimating degradation in water and soil, a QSAR weight-of-evidence approach (ESD, 2006a) was applied using the models shown in Table 3a. Based on these results, the estimated measures for biodegradation indicate that, DMHBP can be considered as persistent in water and soil. Considering both the empirical and modelled data, the half-life in water and soil is expected to be longer than 182 days.

To extrapolate to a half-life in sediments, an approach has been developed using Boethling’s extrapolation factors (BIOWIN v4.02), which involves extrapolating the half life in sediment from that estimated for water (t1/2 water : t1/2 sediment = 1:4). Therefore, in sediments, the half-life is expected to exceed 728 days.
The long-range transport potential (LRTP) of DMHBP from its point of release to air is estimated to be low according to the model prediction presented in Table 3c. The TaPL3 model was used to estimate Characteristic Travel Distance (CTD), defined as the maximum distance traveled by 63% of the substance; or in other words, the distance that 37% of the substance may travel beyond. Beyer et al (2000) have proposed CTD’s of >2000 km as representing high LRTP, 700-2000 km as moderate, and <700 km as low. Based on the result shown in Table 3c, this substance is expected to remain primarily in the areas close to its emission sources.

Table 3c. Model Predicted Characteristic Travel Distance (CTD) for DMHBP

Characteristic Travel Distance Model (Reference)
592 km TaPL3 (CEMC, 2003)

The empirical and modelled data (Table 3a and b) demonstrate that the substance meets the persistence criteria (half-lives in soil and water ≥ 182 days; in sediments ≥365 days) as set out in the Persistence and Bioaccumulation Regulations (Government of Canada 2000).
Potential for Bioaccumulation

Experimental and modelled log Kow values for DMHBP indicate that this chemical has the potential to bioaccumulate in the environment (Table 4a&b).

The experimental BCF values in fish are reported to range from 723 to 5,330 L/kg (NITE Database), indicating that DMHBP has the potential to bioconcentrate in the environment. The bioconcentration tests resulted in a wide range of BCFs, above and below 5000 L/kg at the lowest exposure concentration of 4 ug/L. Bioaccumulation tests performed by the Japanese Ministry of Economy, Trade and Industry (METI), were evaluated for categorization and found to be acceptable.

The Modified GOBAS BAF middle trophic level model produced a BAF of 1,778,279 L/kg (Table 4b). The three other BCF models also provide a weight of evidence to support the bioconcentration potential of this substance. Similar BCF and BAF values were predicted for a structurally similar substance (1,1,4,4-tetramethyl-2-butyne-1,4-diyl)bis[(1,1-dimethylethyl)peroxide] (CAS 1068-27-5).

Table 4a. Empirical data for bioaccumulation

Test Organism Test Concentration Endpoint Value wet wt Reference
Fish 40 ug/L BCF 1410-4160 L/kg NITE Database
Fish 4 ug/L BCF 723-5330 L/kg NITE Database    

Table 4b. Modelled data for bioaccumulation

Test Organism Endpoint Value wet wt Reference
Fish BAF 1,778,279 L/kg GOBAS BAF T2MTL (Arnot and Gobas, 2003)
Fish BCF 40,271 L/kg Gobas BCF T2LTL
(Arnot and Gobas, 2003)
Fish BCF 66,069 L/kg OASIS
Fish BCF 22,233 L/kg BCFWIN v2.15

The modelled bioaccumulation values do not take into account the metabolism potential of the substance. The experimental BCF values confirm that the models are conservative and that metabolism may in fact reduce the bioaccumulation of DMHBP but not always below the bioaccumulation criteria.

The weight of evidence indicates that the substance meets the bioaccumulation criterion (BCF, BAF ≥ 5000) as set out in the Persistence and Bioaccumulation Regulations (Government of Canada 2000).

Ecological Effects

A - In the Aquatic Compartment

There is modelled and experimental evidence that the substance causes harm to aquatic organisms at relatively low concentrations (e.g. acute LC50<1mg/L) [Table 5a and b]. A range of aquatic toxicity predictions were obtained from the various QSAR models considered. Table 5a lists those predictions that were considered reliable and were used in the QSAR weight-of-evidence approach for aquatic toxicity (ESD, 2006a).

Table 5a. Modelled data for aquatic toxicity

Test Organism Type of Test Endpoint Value (mg/L) Reference
Fish Acute LC50 2.76 PNN (AI Expert)
Fish Acute LC50 0.042 ECOSAR
Fish Acute LC50 0.000424 ECOSAR Neutral Organic SAR

Table 5b. Empirical data for aquatic toxicity

Test Organism Type of Test Endpoint Value (mg/L) Reference
Oryzias latipes
(Rice fish)
Acute LC50 (96hr) 4.5 NITE Database

An acute toxicity study on Oryzias latipes (Table 5b) correlated well with the model prediction for DMHBP (Table 5a), with the model being slightly more conservative. The study found a 96 hour LC50 of 4.5 mg/L (NITE Database), while the model predicted an acute LC50 of 2.76 mg/L (PNN). This correlation provides increased confidence in using modelled data for DMHBP and other dialkyl peroxides. Modelling results for acute endpoints suggest that fish will exhibit high toxicity at low concentrations.

These results indicate that the substance is highly hazardous to aquatic organisms (i.e. acute LC/EC50≤1.0mg/L).

B - In Other Media

Table 6. Empirical data for Other Toxicity Endpoints

Test Organism Type of Test Endpoint Value (mg/kg) Reference
Rat Oral LD50 3200-32000 ChemID Plus, 2006 and Kirk Othmer, 2001

The toxicity studies listed in Table 6 have not been evaluated for robustness.

Potential to Cause Ecological Harm

Evidence that a substance is highly persistent and bioaccumulative as defined in the Persistence and Bioaccumulation Regulations of CEPA 1999 (Government of Canada, 2000) together with evidence of commercial activity provides a significant indication of its potential to be entering the environment under conditions that may have harmful long term ecological effects (ESD, 2006b). Substances that are persistent remain in the environment for a long time after being released, increasing the potential magnitude and duration of exposure. Substances that have long half-lives in mobile media (air and water) and partition into these media in significant proportions, have the potential to cause widespread contamination. Releases of small amounts of bioaccumulative substances may lead to high internal concentrations in exposed organisms. Highly bioaccumulative and persistent substances are of special concern, since they may biomagnify in food webs, resulting in very high internal exposures, especially for top predators. Evidence that a substance is both highly persistent and bioaccumulative, when taken together with other information (such as evidence of toxicity at relatively low concentrations, and evidence of uses and releases) may therefore be sufficient to indicate that the substance has the potential to cause ecological harm.

The relatively large importation volumes of dialkyl peroxides into Canada indicate that DMHBP is likely entering the environment in Canada. Once released in the environment, because of its hydrophobicity it will partition to sediments or soils where it will remain for long times due to its resistance to degradation. As it persists in the environment, and because of its lipophyllic character, it will likely bioaccumulate and may biomagnify in trophic food chains. It has also been predicted to exhibit high chronic toxicity to fish. This information suggests that DMHBP has the potential to cause ecological harm in Canada.

Uncertainties

Information on concentrations of DMHBP in the Canadian environment are currently lacking. Yet, the relatively high volume of dialkyl peroxides imported into Canada in 2000 and the reported amount imported in 2005 indicate that there is potential for release to the Canadian environment.

The evidence for high persistence and bioaccumulation potential is considered strong, since both modelled estimates and empirical data indicate that DMHBP meets the criteria set out in the Persistence and Bioaccumulation Regulations of CEPA 1999 (Government of Canada, 2000). Similarly convincing evidence that DMHBP can harm organisms at relatively low exposure concentrations is provided by results of QSAR modelling and supported by experimental toxicity testing for pelagic organisms. However, it must be acknowledged that there were a limited number of empirical studies available relating to the persistence, bioaccumulation and toxicity of DMHBP.

The effects data do not address toxicity in soil and sediments, which have been identified as the primary media of concern based on partitioning estimates. The only effects data identified apply to pelagic aquatic exposures, although the water column is not the medium of primary concern.

The experimental or predicted concentrations, associated with inherent toxicity for aquatic organisms, may have an additional source of uncertainty in some situations, e.g. where these concentrations exceed the solubility of the chemical in water (either experimental or predicted). Given that concentrations for both the toxicity and water solubility often vary considerably (up to several orders of magnitude), it is acknowledged that these uncertainties exist.

There is also uncertainty associated with basing the overall conclusion that DMHBP may be causing ecological harm, solely on information relating to its persistence, bioaccumulation, relative toxicity and use pattern. Typically quantitative risk estimates (i.e., risk quotients or probabilistic analyses) are important lines of evidence when evaluating a substances potential to cause environmental harm. However when risks for persistent and bioaccumulative substances such as DMHBP are estimated using such quantitative methods, they are highly uncertain and are likely to be underestimated (ESD, 2006b). Given that long term risks associated with persistent and bioaccumulative substances cannot at present be reliably predicted, quantitative risk estimates have limited relevance. Furthermore since accumulations of such substances may be widespread and are difficult to reverse, a conservative response to uncertainty (that avoids underestimation of risks) is justified.

References

AI Expert (Artificial Intelligence Expert System). 2005. v 1.25.  Developer: Dr. Stefan P. Niculescu. Copyright © 2003-2005. Environment Canada.

AOPWIN. 2000. Version 1.91. U.S. Environmental Protection Agency. http://www.epa.gov/oppt/exposure/pubs/episuite.htm

Arkema. Products in Everyday Life. Accessed December 14, 2006. http://www.terrainsdentente.arkemagroup.com/telechargement/Arkema_products_va_final.pdf

Arnot, J.A. and Gobas, F.A.P.C. 2003. A Generic QSAR for Assessing the Bioaccumulation Potential of Organic Chemicals in Aquatic Food Webs. QSAR Comb. Sci. 22(3): 337-345.

BCFWIN. 2000. Version 2.15. U.S. Environmental Protection Agency. http://www.epa.gov/oppt/exposure/pubs/episuite.htm

Beyer, A., Mackay, D., Matthies, M., Wania. F, and Webster, E. 2000. Assessing Long-Range Transport Potential of Persistent Organic Pollutants. Environ. Sci. Technol. 34 (4): 699-703.

BIOWIN. 2000. Version 4.02. U.S. Environmental Protection Agency. http://www.epa.gov/oppt/exposure/pubs/episuite.htm

CEMC (Canadian Environmental Modelling Centre) 2003. TaPL3 v. 3.00 model. Released September 2003. Trent University, Peterborough, Ontario. www.trentu.ca/academic/aminss/envmodel.

CEPA 1999. Canadian Environmental Protection Act, 1999. 1999, c. 33. C-15.31. [Assented to September 14th, 1999]. http://laws.justice.gc.ca/en/C-15.31/text.html .

ChemID Plus Lite. 2006. National Library of Medicine Specialized Information Services. http://chem2.sis.nlm.nih.gov/chemidplus/chemidlite.jsp

Cheminfo Services Inc. 2002. Use of Initiators in the Canadian Polymer Resin Manufacturing and Polymer Resin Processing Sectors.

ECOSAR. 2004. Version 0.99h. U.S. Environmental Protection Agency. http://www.epa.gov/oppt/exposure/pubs/episuite.htm

Environment Canada. 2006. Data collected pursuant to subsection 71(1) of the Canadian Environmental Protection Act, 1999 and in accordance with the published notice “Notice with respect to Selected Substances identified as Priority for Action”, Canada Gazette, Part 1, Vol. 140, No. 9

EPIWIN. 2000. Version 3.12 U.S. Environmental Protection Agency.
http://www.epa.gov/oppt/exposure/pubs/episuite.htm

ESD (Existing Substances Division). 2006a. Guidance Module on "Quantitative Structure-Activity Relationships (QSARs)". Guidance for Conducting Ecological Risk Assessments Under CEPA 1999: Science Resource Technical Series, Environment Canada, Internal document available on request.

ESD (Existing Substances Division). 2006b. Issue paper on "Approach to Ecological Screening Assessments for Existing Substances that are both Persistence and Bioaccumulative". Environment Canada. The document may be obtained from the CD entitled "CEPA DSL Categorization: Overview and Results", that is periodically released by the Existing Substances Division, and is also available on request.

Fisher Scientific International Material Safety Data Sheet. 2,5-Dimethyl-2,5-di(tert-butylperoxy)hexane. 10/13/2005. http://www.msdsonline.com

Government of Canada. 2000. Persistence and Bioaccumulation Regulations (SOR/2000-107). Canada Gazette, v. 134. http://www.ec.gc.ca/CEPARegistry/regulations/detailReg.cfm?intReg=35.

HENRYWIN. 2000. Version 3.10. U.S. Environmental Protection Agency.
http://www.epa.gov/oppt/exposure/pubs/episuite.htm

HSDB. 2006. Hazardous Substances Data Bank. http://toxnet.nlm.nih.gov/cgi-bin/sis/search/r?dbs+hsdb:@term+@rn+@rel+110-05-4

Kirk-Othmer Encyclopedia of Chemical Technology. Copyright 2001 by John Wiley & Sons, Inc. http://www.mrw.interscience.wiley.com/emrw/9780471238966/search/firstpage

KOWWIN. 2000. Version 1.67. U.S. Environmental Protection Agency.
http://www.epa.gov/oppt/exposure/pubs/episuite.htm

MPBPWIN. 2000. Version 1.41. U.S. Environmental Protection Agency.
Information available to http://www.epa.gov/oppt/exposure/pubs/episuite.htm

NITE (National Institute of Technology and Evaluation), Japan. 2002. Biodegradation and Bioconcentration of the Existing Chemical Substances under the Chemical Substances Control Law. Available at http://www.safe.nite.go.jp/data/hazkizon/pk_e_kizon_data_result.home_data (accessed October 30, 2006).

Oasis Forecast 2005. Version 1.20. Laboratory of Mathematical Chemistry. Bourgas, Bulgaria.
http://www.oasis-lmc.org

PCKOCWIN. 2000. Version 1.66. U.S. Environmental Protection Agency.
http://www.epa.gov/oppt/exposure/pubs/episuite.htm

SPIN on the Internet. Substances in Preparations in Nordic Countries. Available at http://www.spin2000.net (Accessed August, 2006).

Topkat. 2004. Version 6.2. Accelrys, Inc.
http://www.accelrys.com/products/topkat/index.html

WSKOWWIN. 2000. Version 1.41. U.S. Environmental Protection Agency. http://www.epa.gov/oppt/exposure/pubs/episuite.htm


[1] “Guidelines for the Notification and Testing of New Substances: Chemicals & Polymers (version 2005)”, Government of Canada, Available from http://www.ec.gc.ca/substances/nsb/eng/cp_guidance_e.shtml


Disclaimer: Although care has been taken to ensure that the information found on this website accurately reflects the requirements prescribed in the Canadian Environmental Protection Act (1999), you are advised that, should any inconsistencies be found, the legal documents, printed in the Canada Gazette, will prevail.

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