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Fuel additives
A risk screening of additives
to gasoline and diesel
Contamination of soil, soil air
and groundwater
Teknik og Administration
Nr. 3 2006
CONTENS
1 INTRODUCTION...........................................................................................................5 1.1 Scope............................................................................................................................5 1.2 Organization..................................................................................................................5 1.3 Methods ........................................................................................................................5 1.4 How to read the report...................................................................................................6 1.5 Disclaimer .....................................................................................................................7
2 SUMMARY....................................................................................................................9
3 SAMMENFATNING.....................................................................................................11
4 REGULATIONS ON ADDITIVES IN DENMARK AND THE EU...................................13 4.1 Components and concentrations.................................................................................13 4.2 Classification...............................................................................................................14 4.3 Registration.................................................................................................................14 4.4 Information access ......................................................................................................15
5 THE DANISH FUEL MARKET STRUCTURE..............................................................17
6 ADDITIVES.................................................................................................................19 6.1 Functions and types of additives .................................................................................19 6.2 Typical concentrations of additives..............................................................................20 6.3 New additives..............................................................................................................21 6.4 Historical use pattern of additives................................................................................24 6.5 Producer declared additives in public domain .............................................................27 6.6 “Forensic” additives.....................................................................................................28 6.7 “After market” additives ...............................................................................................29 6.8 Additives found in the environment .............................................................................29 6.8.1 Alkyl lead and MMT.....................................................................................................29 6.8.2 MTBE and alternative oxygenates...............................................................................30 6.8.3 Other fuel additives .....................................................................................................31
7 DATA ON DANISH ADDITIVE CONSUMPTION FROM OPEN SOURCES ................33
8 RISK STRUCTURAL GROUPS AND PROPERTIES OF POTENTIAL ADDITIVES ....39 8.1 Classification...............................................................................................................39 8.2 Distribution ..................................................................................................................40 8.3 Open source based risk survey ...................................................................................42
9 DATA ON ADDITIVES USED BY DANISH PETROLEUM COMPANIES ....................43
10 DATA ON USED ADDITIVES FROM ADDITIVE PRODUCERS .................................45
11 RISK SCREENING .....................................................................................................49 11.1 Risk screening method................................................................................................49
11.1.1 Thresholds for human toxicity or environmental hazard...............................................50 11.1.2 Filter for amounts and concentrations .........................................................................51 11.1.3 Filter for inherent petroleum constituents ....................................................................52 11.1.4 Filter for very volatile components with respect to risk at direct soil exposure .............52 11.1.5 Filter for partitioning to soil air and soil water...............................................................52 11.1.6 Filter for aquifer retardation .........................................................................................53 11.1.7 Filter for aquifer degradation .......................................................................................53 11.1.8 Flow in filter process ...................................................................................................54 11.1.9 Data compilation .........................................................................................................55 11.1.10 Analytical methods for monitoring and control .............................................................57 11.1.11 Testing and discussion of the screening method.........................................................58 11.2 Results of risk screening .............................................................................................61 11.2.1 Classic additives .........................................................................................................63 11.2.2 Surface active additives ..............................................................................................66 11.2.3 Polymers.....................................................................................................................75 11.2.4 Monomers ...................................................................................................................75 11.2.5 Proprietary ingredients ................................................................................................77
12 CONSOLIDATION ......................................................................................................79 12.1 Structural groups of additives with risk for human health or the environment ..............79 12.2 Structural groups of additives with risk for distribution into mobile phases...................79 12.3 Danish additive consumption from open sources ........................................................80 12.4 Risk comparison..........................................................................................................83 12.5 Risk summary .............................................................................................................85
13 CONCLUSIONS AND RECOMMENDATIONS............................................................89
14 REFERENCES ...........................................................................................................93
APPENDIX A ................................................................................................................................ Examples of additive groups and functions .............................................................................101
APPENDIX B ................................................................................................................................ Danish use of potential additives 2001 and their classifications ..............................................111
APPENDIX C................................................................................................................................ Physical-chemical data of potential additives ..........................................................................123
APPENDIX D................................................................................................................................ Distribution of potential additives between soil, air and water..................................................129
APPENDIX E ................................................................................................................................ Template for confidentiality agreement with the 5 Danish petrolium companies……………….135
APPENDIX F ................................................................................................................................ Template for confidentiality agreement with the 5 additive producers…………………………...139
APPENDIX G................................................................................................................................ Key properties used in the risk screening for additive compounds assigned a potential added risk……………………………………………………………………………………………………....143
1 INTRODUCTION
The gasoline additive MTBE (methyl-tert-butylether) has been identified as a major groundwater contaminant at a number of Danish gas stations. A variety of other addi-tives to gasoline and diesel has previously been named /1-3/ but mostly, MTBE is the only additive included in the analytical programs for investigations on fuel spill sites such as gas stations.
Most additives have properties that are different from those of petroleum derived fuel components with respect in particular to polarity (most additive groups) and molecular weight (polymers). Consequently, their fate, e.g.: binding, transport and degradation af-ter spills, may differ from that of the petroleum derived components and in most cases, they are not found with the analytical methods used in routine spill site investigations.
Therefore, the Information Centre on Contaminated Sites (ICC) on behalf of the Danish counties has initiated a screening for additives to gasoline and diesel that may constitute an added risk to soil, soil air and/or groundwater after fuel spills.
1.1 Scope
The main purpose of the screening has been to obtain an early warning in order to en-able timely monitoring for potential risk additives in investigations of gasoline and die-sel spills.
1.2 Organization
The risk screening has been done by DHI Water & Environment supported by a group of experts from the Danish Environmental Protection Agency (DEPA) and Copenhagen Municipality and with the following ICC representatives responsible:
• Arne Rokkjær, ICC (chairman, until August 31st 2005)
• Leo Ellgaard, ICC (chairman, from September 1st 2005).
The section on the Danish regulation and registration of chemicals has been improved by contributions from DEPA.
1.3 Methods
The project has been done in phases with gradually increasing level of specificity of the information. In the first phase, general information on additive use and regulation was compiled from open sources such as the international literature, databases and patent registers, as well as from the registers of consumption as publically available. The com-pounds identified as potentially used fuel additives were evaluated for risk properties
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based upon a simple model describing distribution between soil, air and water and in-cluding official risk classifications.
In the second phase, information on additive products used in Denmark was retrieved from the 5 major Danish petroleum companies and with the help of the Organization of Danish Petroleum Companies. The information was retrieved in the form of lists of ad-ditive products used and supported by safety data sheets for each product. The listing of additive compounds in the additive products proved to be incomplete, as all additive compounds in a product may not be listed in the safety data sheets due to status as mi-nor constitutents, as not classified as hazardous or as proprietary constitutents.
Therefore as the third phase, information on the additive compounds and their proper-ties was compiled from representatives of the five main suppliers of additive products for the Danish market as identified from information on the additive products used in Denmark. One potential supplier refused to provide information.
As the fourth phase, the additive compounds identified through the last two project phases were evaluated in a stepwise risk screening aiming at identifying those com-pounds added to gasoline and diesel that might be associated with an added risk of im-pacting soil, soil air or groundwater. The term added risk means a risk beyond what is associated with consumption and handling of petroleum products in general.
The risk screening as described in section 11 does not pretend to be a full risk assess-ment, but rather an identification of those products and compounds that should be inves-tigated further. The reason for applying a simplified risk screening is that this is the only viable approach to evaluating the almost 100 identified additive compounds due to the large costs of full risk assessments. The details of the risk screening have been submit-ted to the additive producers for commenting before the actual screening was done.
The compilation of information on additive products and compounds from petroleum companies and additive producers has been done subject to confidentially agreements including as one of the most important points that information on additive products and compounds that in the risk screening were not suggested to be associated with an added risk for soil, soil air and groundwater should not be disclosed. Furthermore, all additive producers and the additive producers association (ATC) have had the opportunity to comment upon and add to a draft version of the report. The process is described in more details in section 10.
Whereas the generic information on additives is by nature retrospective (it is based upon the published literature), the intentions in the project have been to provide “snapshots” of the use of additives in Denmark as occurring in 2001 (open source data on use) and 2004 (additive producer data). Accordingly, the project does not pretend to describe the use of additives in general but only within the defined periodes. Other additives than those described here may be in use today and conversely, som additives mentioned may not be used anymore
1.4 How to read the report
This report presents the results of the risk screening in 8 main sections:
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First phase:
• Regulations and registration of additives
• The Danish fuel market structure
• General information on additives
• Open source information on Danish additive consumption
• Risk properties of additives
Second phase:
• Information on Danish consumption from petroleum companies
Third phase:
• Information on Danish consumption from additive producers
Fourth phase:
• Risk screening
• Consolidation of risk information
• Conclusions and recommendations.
Detailed tables with technical and chemical information are compiled in appendices.
1.5 Disclaimer
The risk screening has been entirely dependent upon access to valid and documented data on additive identities and properties. Erroneous risk identification due to lack of such data is not the responsibility of the authors. Furthermore, the risk screening has been based upon the assumptions and conditions made in the report intending only to identify those additive compounds that should be investigated further. The authors can not be made responsible for any conclusions and consequences beyond this.
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2 SUMMARY
Additives are added to fuels such as gasoline and diesel and in case of spill, some of these may imply an added risk to soil, air and groundwater as compared to the spill of petroleum derived fuel components only. Therefore, an inventory has been performed based upon both open (2001) and confidential (2004) sources of information in order to exclude from consideration all such gasoline and diesel additive compounds that do not imply an added risk in case of a fuel spill. In the context of this report, additives include oxygenates (blending products excluding petroleum fractions), functional additives and performance additives.
The inventory of potential risk additives show that for some additives, classification data were not complete. The information on additives classified as dangerous was furthermore not com-plete in the Danish registers. The limited public access to information on additives may in part be due to this being considered highly proprietary by additive producers and petroleum companies. Thus, data retrieved from open sources can be considered to give only part of the picture of Dan-ish fuel additive consumption and risks. Furthermore, the main focus for new additives is now upon polymers and surface active additives and for these additive groups, property data are less readily available than for the “classic”, simple additive compounds.
Previous experience with additives suggest that using elements such as lead or manganese of po-tential human health and/or environmental concern as fuel additives should be considered care-fully, as emission with exhaust can not be avoided. Furthermore, the use of compounds with high water solubility, high vapour pressure, slow biodegradation and/or serious human health or envi-ronmental hazard as additives will require special caution.
Proprietary information on additives used in Denmark from the 5 Danish petroleum companies and the 5 major suppliers of additives to the Danish market, in all 95 additive compounds in 34 additive products, showed that additive compounds classified as toxic or very toxic were not de-clared used as additives in Denmark, whereas totally 10 additives classified as very environmen-tally hazardous were used in Denmark. Some additive compounds were not identified (21) and/or not associated with the property data and classifications needed in risk screening (9).
Screening of additives used in Denmark for potential risk compounds was done as a filtering process removing those compounds that will with high probability not be of added risk (com-pared to the inherent gasoline or diesel constituents) after a spill with soil, air and groundwater as the end points considered and with thresholds based upon Danish maximum contaminant con-centrations and levels. Thus, the screening process was not a full risk assessment and accord-ingly associated with the added uncertainty and precaution required in a simple screening ap-proach with limited data available. Also, the screening process was not an identification of all potential risk compounds used as fuel additives, but should be considered a removal from future investigation programs for fuel spills of those compounds that are probably not associated with added risk.
A list of 8 additive compounds of potential risk to groundwater in case of fuel spill was estab-lished, and for one additive compound, a risk for air was suggested as well. Only two of these additives were classified as very environmentally hazardous. For these additive compounds, it is suggested to launch a full risk assessment including scenario based assessments of the risks for groundwater and air associated with fuel spills in Denmark, and furthermore to investigate the
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historical and present use of these compounds and to include those used over longer periods or still used in the monitoring programs at fuel spill sites.
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3 SAMMENFATNING
Benzin og diesel tilsættes additiver, der teoretisk set kan udgøre en øget risiko for jord, luft og grundvand ved spild, set i forhold til spild af benzin og diesel uden additiver. Der er derfor gen-nemført en gennemgang af additiver tilsat benzin og diesel i Danmark i årene 2001 og 2004 ba-seret på henholdsvis oplysninger fra åbne kilder og oplysninger fra danske benzinselskaber og additiv producenter med salg til Danmark. Formålet har været at belyse adgangen til information om additiver, samt at afgrænse de stoffer, der kunne udgøre en øget risiko ved spild. I denne rap-port omfatter begrebet additiver oxygenater og additiver tilsat på raffinaderiet og på depoter, men ikke delfraktioner eller –produkter af olie.
Gennemgangen viste, at for nogle additiver mangler dele af de data, der benyttes til klassifice-ring af risiko for miljø og mennesker, samt at ikke alle anvendte additiver med klassifikation som farlige kunne findes i de danske registre. Den manglende information kan tildels skyldes, at disse oplysninger betragtes som fortrolige af forretningsmæssige hensyn. Derudover udvikles nu hovedsagligt nye additiver indenfor grupperne af polymerer og overfladeaktive stoffer, hvor dis-se data kan være vanskelige at fremskaffe. Åbne kilder kan dermed ikke give et dækkende bille-de af risikoen ved brug af additiver i benzin og diesel.
Generelt viser erfaringerne med brug af additiver, at tilsættes brændstof grundstoffer som bly eller mangan, der er farlige for mennesker eller miljø, bør risikoen herved undersøges. Derud-over er der behov for grundig undersøgelse af brugen af organiske tilsætningsstoffer, der har høj vandopløselighed, højt damptryk, lav bionedbrydelighed eller stor giftighed overfor mennesker eller miljø.
Oplysninger fra de 5 største benzinselskaber og de 5 mest betydende leverandører af additiver til brændsel i Danmark, i alt om 95 additiv stoffer i 34 additiv produkter, viste, at stoffer klassifice-rede som giftige eller meget giftige ikke blev opgivet som anvendt, mens 10 stoffer med klassifi-kation meget miljøfarlige blev anvendt. Nogle additiv stoffer (21) blev ikke identificeret, og for nogle (9) manglede oplysninger til den efterfølgende risiko screening.
Risikoscreening blev udført som en filtrering, der fjernede de additiv stoffer, der ikke udgør en ekstra risiko, set i forhold til brændstofkomponenterne selv. Risikoen i forhold til luft, jord og grundvand blev inddraget, og det danske beskyttelsesniveau (kvalitetskriterier) blev taget som udgangspunkt. Risikoscreeningen er altså ikke en fuld risikovurdering, og der er benyttet en række forsigtige forudsætninger, således som det er nødvendigt, når datamaterialet er begrænset. Det skal bemærkes, at der snarere er tale om en frasortering af “ikke-risiko-stoffer” end om en identifikation af “risiko-stoffer”. Derudover skal fremhæves, at udgangspunktet for screeningen er additiv stoffernes anvendelse i brændstof, og resultaterne kan derfor ikke benyttes for andre anvendelser.
Risikoscreeningen resulterede i en liste på 8 additiv stoffer, hvor en øget risiko for grundvand ved spild ikke kunne udelukkes, samt desuden for ét af stofferne en mulig risiko for luft. Kun 2 af stofferne var særligt miljøfarlige. Det foreslås at gennemføre en fuld risikovurdering for disse 8 stoffer, hvor vægten lægges på scenariebaseret vurdering af risikoen for grundvand og luft. De-suden forslås det at undersøge stofferne forbrugshistorie i Danmark og på den baggrund inddrage additiv stoffer benyttet over længere tid eller stadig benyttet i de rutinemæssige undersøgelser af spild af benzin og diesel.
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4 REGULATIONS ON ADDITIVES IN DENMARK AND THE EU
A status based upon current regulations is given, but any impact to be foreseen during the implementation of the new European Union (EU) regulation of chemicals (REACH) is not considered.
4.1 Components and concentrations
The regulations on composition and properties of gasoline and diesel in Denmark give maximum contents of oxygenates in gasoline /4;5/:
• Methanol: <3% v/v1
• Ethanol: <5% v/v
• iso-Propanol: <10% v/v
• tert-Butanol: <7% v/v
• iso-Butanol: <10% v/v
• Ethers2: <15% v/v
• Other oxygenates3: <10% v/v.
The maximum oxygen content is 2.7% w/w4 in the gasoline. Lead addition is not al-lowed, and the natural lead content of the gasoline must be below 0,005 g/L /4;5/. In addition, the regulations provide maximum contents of petroleum constituents (e.g.: aromatics, olefins, sulphur) as well as technical requirements (e.g.: octane numbers, dis-tillation properties) /4;6/.
According to an agreement between the Danish Environmental Protection Agency (DEPA) and the Danish Petroleum Industry Association (OFR), methyl-tert-butylether (MTBE) has not been used in 92 and 95 octane gasoline since 2001 in Denmark, and 98 octane gasoline with MTBE is only distributed from a limited number of gas stations equipped for advanced leak prevention /7/. Furthermore, other ethers than MTBE are not added to gasoline in Denmark as oxygenates /7/.
Additives to diesel are not regulated, but again there are maximum contents for petro-leum constituents (e.g.: polycyclic aromatic hydrocarbons, sulphur) as well as technical requirements (e.g.: cetane number, distillation properties) /4;6/.
1 % v/v: volume percent 2 Defined as ethers with 5 carbon atoms or more as e.g.: MTBE 3 Defined as other monoalcohols 4 % w/w: weight by weight percent
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A reduction in maximum contents of aromatics and sulphur effective in full from Janu-ary 1st 2009 /6;8;9/ may imply an increased requirement for additives in order to satisfy the technical requirements and maximum contents.
All gas oil and kerosene sold in the EU exempt from tax or subject to reduced tax must be marked with a dye (Solvent Yellow 124) /10/ and in Denmark, an additional dye (C.I. Solvent Blue) must be added to fuel as a further fiscal marker /11/. It has been considered to add further dyes to fuels in order to enable dating of spills /12/ but this “forensic” marking has not been implemented.
The EU member states must monitor the composition of gasoline and diesel with re-spect to the above mentioned properties including oxygenate contents and report the monitoring data with summaries of national consumption of specified categories of fuel /13/.
4.2 Classification
It is mandatory for all producers/importers of chemical compounds and products to ac-quire the information required to evaluate whether the compounds or products are dan-gerous after classification as defined in /14;15/, compare also /16;17/. The hazards con-sidered for classification are danger of explosion and fire, human health and environmental hazard.
Compounds found on the List of Dangerous Substances /18/ provided by the DEPA are considered dangerous without further evaluation but for other compounds, classification must be done by the producer/importer. Compounds present in products at concentra-tions below 0.1% (toxic, very toxic, carcinogenic, mutagenic, reprotoxic or very envi-ronmentally hazardous) or 1% (other danger classifications), 0.02% and 0.2% respec-tively for gaseous preparations, shall not be considered in classification /14/.
Examples of references for official classifications and property data are the EU EINICS and ELINCS lists, see below, as available from the ESIS web site (http://ecb.jrc.it/esis/), the US EPA High Production Volume Challenge Program Robust Summaries and Test Plans as available from the US EPA web site (http://cfpub.epa.gov/hpv-s/) and the Envi-ronmental Health Criteria (EHC) Monographs available from the International Pro-gramme on Chemical Safety (IPCS) web (http://www.inchem.org/pages/ehc.html).
4.3 Registration
New chemicals must be notified to the Danish Environmental Protection Agency (DEPA) if imported or produced above 10 kg/year/producer in the whole of the EU /19/. New chemicals are defined as those chemicals not registered before September 18th 1981 in the European Inventory of Existing Commercial Substances (EINECS) /20/. The notification must include information on physico-chemical, environmental and health properties of the substance, unless this information has already been notified in another EU member state. Information on new chemicals already notified is registered in the European List of Notified Chemical Substances (ELINCS) /20/.
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If a new chemical has been notified in another EU member state, the importer/producer need only to inform the DEPA on the import/production and that the substance has been notified already in the EU /19/.
All import/production of compounds classified as dangerous must be notified to the DEPA /14/.
Dangerous, see section 4.2, products produced or imported above 100 kg per year and used in the working space /21/ must be notified to the Danish Product Register /22;23/ operated in common by the Danish Environmental Protection Agency (DEPA) and the Danish Working Environment Authority (AT) /24/ In addition to products classified as dangerous, also products with higher than 1% contents of compounds assigned an occu-pational exposure limit (OEL) by the AT and/or classified as dangerous compounds must be notified to the Product Register.
Petroleum products are generally considered one “compound” as they are “natural mix-tures” or the result of a chemical process producing mixtures /15/ and considered exist-ing chemicals if found in the EINECS list. The Hydrocarbon Solvents Producers Asso-ciation has produced a suggestion for environmental classification of 22 petroleum “compounds” with a description of the principles suggested for the classification /25/.
Compounds added to a mixture intentionally, such as most fuel additives, are consid-ered constituents in products and not parts of the “compound” or “natural mixture” and must thus be classified and notified separately as described above /15/. In case of changes in composition or concentrations above specified limits of a product, a new evaluation of the product properties must be done /15/, but all changes must be regis-tered /19/.
4.4 Information access
The information in the Danish Product Register is available for users of chemicals and products as well as for authorities and researchers /24/, i.e.: there is open access. The access is obtained via the web site of the Product Register /26/. Access to the national product registers from Denmark, Norway, Sweden and Finland can be obtained from the web site Substances in Preparations in Nordic Countries (SPIN) /27/.
Parts of the information in the Product Register can be kept confidential at the request of the notifier /24/ but for new compounds, information on chemical identity, purity, additives, human health and environmental classifications can not be kept confidential /19/. After 10 years, the confidential information is made available unless the notifier renews the claim on confidentiality /24/.
The Product register web access allows for retrieval of information with product name or compound information (name, CAS5 number, EC6 number or molecular formula) as keys, but not with use categories (e.g.: fuel additives). The information available is pri-marily the standardized risk phrases and notification on lists such as ELINCS, EINECS, the DEPA List of Dangerous Compounds, the Montreal Protocol etc. Data retrieval with
5 CAS: Chemical Abstracts 6 EC: European Community
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compound use categories as key in the Product Register is possible from the DEPA or the AT, but due to the confidentiality requirements, the limitations in the registration re-quirements and the access limitations, see also section 4.3, the accessible additional in-formation is limited.
The Nordic web site Substances in Preparations in Nordic Countries (SPIN) additionally allows for information retrieval based upon use categories as national, Nordic or EU use categories, and upon industrial area codes. The most important additional information available from SPIN is the national and Nordic, annual consumption totally and within use categories of dangerous compounds. The previously mentioned confidentiality re-strictions on e.g.: use category of a compound apply for the SPIN database as for the parent Nordic databases, but the restrictions are implemented differently in the different countries allowing for cross checks of compounds and use categories.
The supplier of a dangerous compound or a product is required to provide a chemical safety data sheet (SDS) describing the properties (technical, environmental, hazards) with standardized contents and format /22/. As a compound in a product is classified as dangerous based upon a combination of compound properties and concentration, minor components below specified limits will generally not be declared in the product SDS.
To highlight the access to and coverage of information on fuel additives used in Den-mark from official registers, it can be mentioned that information retrieval from the PR and the SPIN databases identified totally 25 additive compounds used in Denmark in 2001. The declaration of additive compounds used in products sold in Denmark pro-vided by the additive producers listed 95 compounds. Accordingly, information on the remaining 70 compound was not available from the PR and SPIN databases. Among explanations are that some compounds are not new, are not dangerous or are subject to confidentiality, compare sections 4.2, 4.3 and 4.4.
It should be mentioned here, that all fuel additives imported to or manufactured in the US or Canada must be registered with the United States Environmental Protection Agency (US EPA) or Environment Canada, respectively. Accordingly, it is possible to require and obtain full registration of additives, if this is incorporated into legislation.
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5 THE DANISH FUEL MARKET STRUCTURE
The total Danish consumption in 2003 was 2,600,000 m3 of gasoline and 2,400,000 m3
of diesel. Two Danish refineries supplied the major part of the Danish fuel market, with minor contributions from import of refined products. Five Danish petroleum companies dominated the market with almost equal market shares, Figure 5.1.
Refineries outside Denmark are used only by one of the 5 major petroleum companies and by some of the smaller petroleum companies (market shares each <10%). Further-more, the distribution of the fuel products is from a limited number of depots, some of which are joint operations for more than one company.
Figure 5.1 Market shares for Danish suppliers of gasoline and diesel /28/.
0
5
10
15
20
25
30
Mark
et
sh
are
(%
)
Shell Statoil HydroTexaco
Q8 OK Others
Gasoline Diesel
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6 ADDITIVES
Additives are compounds added intentionally to gasoline and diesel (and other petro-leum products such as heating oil and lubricants) in order to improve the performance and/or sales of the fuels. The rationale for using additives can thus be fivefold:
• Improving handling properties and stability of the fuel
• Improving combustion properties of the fuel
• Reducing emissions from the fuel combustion
• Protection of the engine
• Branding of the fuel product.
Conventionally, additives added to high concentrations (typically >1%) at the refinery are called blending components, additives added to lover concentrations (typically <1%) at the refineries are called functional additives, and additives added to the lower concen-trations at depots and terminals by the companies are called performance additives. In the context of this report, all three types of additives are simply referred to as “addi-tives”, and both blending components and functional additives are refered to as refinery additives. In addition to these additives, additive mixtures are also sold for use with each consumer: “after market products” or “secondary products”. Blending components are mainly oxygenates and petroleum fractions, whereas functional and performance additives are mainly mixtures of chemical compounds dissolved in solvents.
Blending components (mainly oxygenates) as well as functional and performance addi-tives are part of this inventory on gasoline and diesel additives whereas petroleum frac-tions are not, as they are considered subfractions of the fuel with comparable properties.
In order to retrieve information on the use of additives to fuel, a literature search was conducted in the open databases, and the obtained information is used in the subsequent sections.
6.1 Functions and types of additives
In Appendix A, examples of additives to gasoline and diesel are summarized after pur-pose of use and function, as reported in text books and reviews /1-3;29-36/. The sum-mary is by no means complete, partly because the variety of additive compounds used is large, partly because parts of the information on identity of additives are proprietary. Furthermore, the summary is by nature retrospective as it is based upon published text books and review literature. Finally, the use of additives exhibits an extreme variability in response to differences in market requirements, market supplies, product prices and supplier availabilities. Therefore, only a small fraction of the additives summarized in Appendix A needs to be used in each country, and many other additives may in reality be used. The absence of specific compounds as examples of additives from several functions reflects the proprietary nature of the information on additive identity.
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The required reduction of the contents of aromatic compounds in gasoline, see section 4.1, will demand an increase in contents of oxygenates or other high octane components in the gasoline. The requirement for addition of anti corrosives and metal deactivators is increasing with the higher contents of oxygenates in the fuels due to the corrosive effect and the ability to solubilize metals of the oxygenates.
With reduced quality of diesel products from lower quality raw petroleum or from cracking of higher boiling petroleum fractions, the requirement for cetane improvers will increase. Also, in a future use of e.g.: alcohols for biodiesel, addition of cetane im-provers to % concentrations may be required.
Surfactants are used as additives with a range of different functions such as e.g.: preven-tion of particle formation, dispersion of water, formation of protective layers on sur-faces, increase in electric conductivity and reduction of surface tension.
Further discussion of the purposes and functions of additives is outside the scope of this report and they are thus not further described here, but most additives belong to a few main structural/functional groups:
• Short chain alcohols and ethers
• Complex binders
• Metalorganic compounds
• Heteroorganic compounds
• Oxidizing organic compounds
• Petroleum fractions
• Surfactants
• Polymers.
Whereas the addition of petroleum fractions will change the overall fuel composition and hydrocarbon distribution, these compounds are not fundamentally different from other fuel constituents. The structural properties of the remaining main groups are, as stated before, different from the properties of other fuel constituents either with respect to molecular weight (most polymers) or to polarity (other groups, some polymers).
6.2 Typical concentrations of additives
The concentrations of additives in fuels are not regulated besides the requirements stated for oxygenates, lead and dyes, see section 4.1.
Oxygenates are the only additives, besides petroleum fractions, that are found in % con-centrations in fuels. Typical concentrations of selected groups of additives are given in Table 6.1.
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The concentration of alkyl leads in gasoline in the US was initially just below 0.1 % and dropped to approximately 0.01 % in the last years of use, whereas the lead scavengers were present in the range 0.01-0.03 % /38/, see also sections 6.2 and 6.6.
Additive purpose Gasoline Diesel
Oxygenates 5 - 15 % None7
Cetane improvement None 0.01 – 0.1 %
Anti-icing 0.1 - 2 % 50 ppm - 0.01 %
Demulsification 1 - 10 ppm8 60 - 80 ppm
Anti-corrosion 5 ppm -0.01 % 10 - 20 ppm
Metaldeactivation 5 - 10 ppm 10 ppm
Flow improvement None 50 ppm – 0.1 %
Anti-foam None 1 - 10 ppm
Antistatic None 1 - 50 ppm
Deposit control 0.01 – 0.1 % None
Anti-oxidation 10 ppm - 0.01 % 10 - 15 ppm
Lubricants 25 ppm - 0.05 % 25 ppm - 0.05 % Table 6.1 Typical concentrations of selected groups of additives to gasoline and diesel given as ppm w/w
9
/30;33;37/.
The additive concentrations are considered highly proprietary, and the treat levels will to a very large degree depend upon the product, the fuel distributor, the refinery and the additive producer but the main feature is that additive concentrations are:
• Oxygenates 1 – 10 %
• Anti-icing additives 0.1 - 1 %
• Cetane improvers 0.1 %
• Other additives 1 ppm – 0.1 %.
Polymers and surfactants are generally added to concentrations in the upper end of the 1 ppm to 0.1 % range.
Additionally, petroleum fractions and petroleum derived solvents are frequently applied to concentrations from ppm to the high % range.
6.3 New additives
The number of new, original patents on fuel additives per year is approximately 500 with most patents emphasizing gasoline and diesel additives /39/. From the distribution of new patents among different types of additives, Figure 6.1, it can be seen that a large number of new surfactants are developed for additive use in fuels.
7No information in the references given or not relevant for the fuel product in question 8 ppm: parts per million, mg/L or mg/kg, 1% is 10,000 ppm 9 w/w: weight by weight
21
Besides surfactants, flow improvers (mostly polymers) and combustion catalysts (mostly metalorganic compounds) were the most frequently patented fuel additives in this period (1990-1999).
As examples of “new” additives proposed for use in gasoline and diesel, compounds from published papers and patents are listed in Table 6.2. Papers may describe the use of well known additives in new formulations, and patents may refer to a new country of patenting for well known additives, but replicates from the list given in Appendix A are deleted from Table 6.2. It should be noted, that publication of a proposed additive does not necessarily mean, that the additive has in reality been applied as a fuel additive but only, that the compound has been considered for additive use.
Figure 6.1 Distribution of fuel additive patents between additive groups 1990-1999 /39/.
In a number of papers on e.g.: additive effects, the descriptions of the additive identities are not specific. Descriptions such as “polar ether amine based additive packages XYZ-1” /54/ are not uncommon and do not allow for unequivocal identification of the addi-tive compound behind the abbreviation. Still, useful information on the additive struc-tures under consideration may be extracted:
• Polyalkoxylates of alkylamine (deposit control) /55/
• Mixtures of alkylpolyethoxylates or alkylarylpolyethoxylates with alkylglycol ethers (combustion catalysts) /56/
• Metalsalts (Li, Na, Fe, Co, Ni, Ce, Mo, W, La) of C3 – C50 organic acids (combus-tion catalysts) /57/
0
10
20
30
40
50
% o
f fu
el
ad
dit
ive
pa
ten
ts
Surfa
ctan
ts
Flow im
prov
ers
Antioxida
nts
Antikno
ck a
dditive
s
Cet
ane
impr
over
s
Com
bustio
n ca
talysts
Oth
ers
22
• Mixtures of C7 – C29 carboxylic acids and ethanolamine, propanolamine or isopro-
panolamine (lubricants) /58/
• Alkali- or earthalkalimetalsalts of carboxylic acids, carbonic acid or boric acid (anti-wear) /59/
• Mixtures of dimethyldithiocarbonate, acetaldehyde and ethylnitrate (cetane im-pover) /60/
• Mixtures of a reaction product of 4-alkyl-2-morpholinone and an alkylphenoxy-polyalkoxylamine and a reaction product of polypropylenoxidediamines and triethylentetraamine (deposit control, demulzifier/dehazer) /61/.
• Reactionproducts of alifatic carboxylic acids and polyoxyalkylenediamines (cetane improver) /62/
• Lactones of polyisobutenylsuccinic acid (deposit control) /49/.
Purpose Compound Reference
Not specified Dioctylphthalate /40/
Not specified 2-Ethylhexanecarboxylic acid /40/
Not specified Zirconium 2-ethylhexyloctanoate /40/
Antiknock 2,4,4-Trimethyl-1-pentene /41/
Antiknock 2,4,4-Trimethyl-2-pentene /41/
Antioxidant 2,4,6-Tri-t-butyl-3-pentadecylphenol /42/
Cetane improver Heptylnitrate /43/
Cetane improver Hexylnitrate /43/
Cetane improver Diethylbicyclopentadienyl iron /44/
Cetane improver Di-t-butylperoxide /45/
Cetane improver Tetralinehydroperoxide /46/
Combustion cata-lyst
Methylpyruvate /47/
Deposit control Di-(2-hydroxyethyl)ethyloctadecylammonium sulfat
/48/
Deposit control 1-(2-Aminoethyl)piperazine /49/
Dye 1-[2-Methyl-4-[(2-methylphenyl)azo]phenylazo]-2-naphtenol
/50/
Dye 1,4-Bis[(1-methylethyl)amino]anthraquinone /50/
Oxygenate Diethylcarbonate /51/
Oxygenate 2,3-Butanediol /52/
Oxygenate Dimethylcarbonate /51/
Oxygenate Methylethylcarbonate /51/
Oxygenate 1-t-Butoxy-2-propanol /53/
Oxygenate Dimethyldicarbonate /51/
Table 6.2 Examples of additives proposed for use in gasoline and diesel in published papers and patents.
Most patents are taken by the large petroleum companies and additive producers such as e.g.: Texaco, Chevron and Lubrizol. In the literature search, Texaco came out with the largest number of patents taken. If it is anticipated that the larger companies and pro-ducers are most likely to introduce their patents on the market, the following “new” ad-ditive structures are most likely to occur in additive products:
23
• Surfactants with polyalkoxylate, amino and alkyl groups (Texaco, Nippon, Lubri-zol)
• Surfactants with amid and alkyl groups, in some cases with a polymer sidechain (Elf, Mobil, Texaco)
• Surfactants with polyalkoxylate, alkyl and heterorganic (piperidine or morpholine derived) groups (Texaco)
• Longchain amines (Exxon and Chevron)
• Polyalkoxylates, glycols and nonylphenol polyalkoxylates (American Energy)
• Oxygenates such as alternative alkylnitrates, tetralinehydroperoxide and alkylcar-bonates (Nippon, Mitshubishi, Union Oil)
• Other structures such as polysuccinimides, metalsalts (alkali and earthalkali car-boxylates, carbonates and borates) and alkanolamines (BP, Lubrizol, Texaco).
Several newer additives are polymers with molecular weight in the range of 300 to 10.000 g/mole (D, Dalton).
6.4 Historical use pattern of additives
The development and application of additives has responded to technical and regulatory requirements over the last century, see Figure 6.2.
As an example of the factors impacting the use of additives it can be mentioned, that al-kylleads were introduced as gasoline additives in 1926 as antiknock agents (octane im-provers), i.e.: as a response to a technical requirement and enabling the use of a broader range of gasoline qualities. Later it was found that alkylleads also protects exhaust valve seats and thus have an anti-wear function. In 1927-1928, 1,2-dibromoethane and 1,2-dichloroethane were introduced to counteract the formation of lead precipitates in the combustion chamber, exhaust valves and at spark plugs. Lead was added as lead addi-tive packages containing tetraethyllead, triethylmethyllead, dimethyldiethyllead, trimethylethyllead and tetramethyllead but from approximately 1980, mostly tetra-ethyllead was used /63/. The lead concentrations in US gasoline were initially in the range of 0.7-1 g/L but in response to the increasing concern regarding the lead pressure upon the population, the legal maximum concentrations were decreased to 0.25 g/L in 1982, 0.1 g/L in 1985, 0.02 g/L in 1986 and finally, a ban of lead additive addition was enforced in the US in 1996 /64/. Since the year 2000, lead addition to gasoline has been banned in the European Union /9/, i.e.: as a human health based regulatory intervention. Also, over time the primary function of lead additives changes from antiknock to anti-wear, partly in response to the required decrease in legal maximum lead concentrations in the gasoline.
In response to the phase out of alkylleads, oxygenates such as methyl-tert-butyl ether, MTBE, were introduced for antiknock purposes in the early 1980s i.e.: as a response to a technical requirement activated by the above mentioned regulatory intervention. Ex-periments with use of shortchain aliphatic alcohols and ethers (methanol, ethanol, tert-
24
butanol, methyl-tert-butyl ether, methyl-tert-amyl ether) had at that time been going on for more than 100 years aiming at the fuel effect of the addition and in 1987/88, oxy-genate addition to gasoline was used for the first time in a US state program to reduce air pollution (“reformulated gasoline”) /63/, i.e.: as a response to a regulatory inter-vention.
Figure 6.2 Production period for additives with selected purposes /30/.
The oxygenates most frequently used in the US are /65;66/:
• Ethanol
• Methanol
• tert-Butyl alcohol (TBA)
• Methyl tert-butyl ether (MTBE)
• Methyl tert-amyl ether (TAME)
• Ethyl tert-butyl ether (ETBE)
• Di-iso-propyl ether (DIPE).
Still, other ethers and alcohols of the same structural properties are used /67/. The re-quirement for addition of oxygenates in terms of “reformulation” differs from county to county and from state to state in the US /66/.
In the EU, ETBE is moving in to take over the role of MTBE, in part helped by a EU di-rective setting requirements for the use of biofuels in the EU /68/. Here, ETBE is claimed to be a biofuel when produced in part with bioproduced ethanol as raw mate-rial, and ETBE is now used in the same amounts as MTBE in Germany /69/.
1910 1930 1950 1970 1990 2010
Cetane improvers
Antiknock
Antioxidants
Metal deactivators
Anti-icing
Antistatic
Lubricants
Demulsifiers
Surfactants
Antifoam
25
An example of the flow in development of additive use is shown in Figure 6.3 for anti-knock additives. In the figure, an EPA waiver is a permit issued by the US EPA for use of the compounds as fuel additives, see also sections 6.8.1 and 6.8.2 for further explan-antions.
Evidently, the additives used in gasoline and diesel are selected in response to a combi-nation of technical, regulatory, environmental and economical incentives, although the details of the development will differ between additive groups and countries.
Figure 6.3 Development in antiknock additivation, an example from the US /65/.
26
6.5 Producer declared additives in public domain
For a few of the additive producers, information on the additive compounds used can be found on their homepages,Table 6.3.
Purpose Compound Producer
Antiknock Methylcyclopentadienyl mangananese tricar-bonyl, MMT
Ethyl
Deposit control 1,2-Diaminoethane Huntsman
Deposit control N-(2-Aminoethyl)-1,2-ethandiamine Huntsman
Deposit control 2-[(2-Aminoethyl)amino]ethanol Huntsman
Deposit control N,N’-Bis-(2-aminethyl)-1,2-ethandiamine Huntsman
Deposit control N- (2-aminoethyl)-N'-{2- (2-aminoethyl)amino}ethyl}-1,2-ethanediamine
Huntsman
Deposit control N,N’-Bis-(2-aminoethyl)piperazine Huntsman
Deposit control N-[(2-aminoethyl)2-aminoethyl]piperazine Huntsman
Deposit control 4- (2-aminoethyl)-N- (2-aminoethyl)-N'-{2- {(2-aminoethyl)amino}ethyl}-1,2-ethanediamine
Huntsman
Deposit control 1-[2-[[2-[(2-aminoethyl)amino]ethyl]-amino]ethyl]-piperazine
Huntsman
Deposit control 1- (2-aminoethyl)-4-[(2-aminoethyl)-amino]ethyl]-piperazine
Huntsman
Table 6.3 Examples of additive compounds declared on producer web pages.
Additionally, one producer (BASF) supplies information on one of the types of addi-tives used:
• Polyisobutyleneamines and polyetheramines.
One producer (Chevron/Oronite) provides generic information on additives used in gasoline and diesel without specific references to the additive compounds used in their products.
Most producers provide information on the additive products and their use only, not on the active additive compounds, on their web pages:
• Octel
• Chevron/Oronite (provides compound information on additives to lubricants)
• Crompton
• Lubrizol (provides compound information on additives to lubricants)
• Shell
• Ondeo Nalco.
Evidently, the number of companies declaring the active compounds in their products is limited, and the number of additive compounds declared is also small, compared to the large number of compounds used, see section 10.
27
The Technical Committee of Petroleum Additive Manufacturers in Europe (ATC) pro-vides three documents listing additive compound groups and examples on their web page /30;70;71/.
The very limited public information on the identities of additive compounds and on the composition of additive products is probably due to he large economical interests asso-ciated with production of the fuels and the additives.
6.6 “Forensic” additives
Additives to fuels are to some extent used to establish the origin and age of a fuel spill in liability cases, i.e.: in environmental forensics.
Purpose Compound Period of use in the US
Tetraethyl lead
Tetramethyl lead
Methyltriethyl lead
Dimethyldiethyl lead
Trimethylethyl lead
1923 - 1996 (-1992 in California)
Dicyclopentadienyl iron -10
Iron pentacarbonyl -
Methylcyclopentadienyl manganese tricarbonyl, MMT
1958-1985
Antiknock
Nickel carbonyl -
Biocide 2-Methoxyethanol -
1,4-Diisopropyl aminoanthraquinone
4-Diethylaminoazobenzene
Azobenzene-4-azo-2-naphtol
Dyes and markers
Benzene-azo-2-naphtol
-
Flow improver
Polybutene 1982 (Part of Chevron sur-factant mixture)
1,2-Dibromoethane Lead sca-venger 1,2-Dichloroethane
1927-
2-Propanol -
Di-iso-propylether -
Ethanol 1975 – (Nebraska since 1930)
Ethyl-t-butylether, ETBE 1993-
Methanol 1979-
MTBE 1979-
tert-Amylethylether, TAEE 1993-
tert-Amylmethylether, TAME 1995 -
Oxygenate
tert-Butanol (TBA) 1969 -
Table 6.4 Additives to gasoline and diesel commonly used in environmental forensics, US based /63;64;72;73/.
Therefore, textbooks and review papers on environmental forensics list use patterns of common fuel additives, see Table 6.4 for a short summary. Similar information has not been identified for Denmark from open sources.
10 -: use period not specified
28
The most commonly used forensic markers are the alkyl leads, the dihaloethanes and the oxygenates, because use patterns for these compounds are either based upon or derived from regulatory requirements and waivers.
The use of the large number of other fuel additives for forensic purposes is hampered by the proprietary nature of the additive compounds, their complex chemical structures (i.e.: chemical analysis is difficult) and the common use of the same compounds in many fuel products /63/.
6.7 “After market” additives
A large variety of octane boosters and performance improvers was found in a search of the web. These products are primarily sold on the web or from the gasoline stations and are added to the gasoline or diesel by the consumer, i.e.: “after market” of the fuel itself. Similar products are used by some garages in order to obtain a short term motor per-formance improvement. Generally, the additive compounds in these products are not declared on the web.
“After market” additives are advertised by Chevron/Oronite on their homepage without declaration of the additive compounds in the products.
Purchase of two products was possible from a Danish gasoline station selected at ran-dom in Copenhagen. The additive compounds present were not declared in details, but an octane booster was declared to contain MMT, see section 6.8.
It must be expected that the “after market” additives are used in Denmark, but informa-tion on the annual sales volume is not available. Still, it would be expected that the use of “after market” products is small compared to the use of additives sold with the fuel products. The identities of the additive compounds in “after market” products are ex-pected to reflect the additives generally used worldwide, but may be different from those added to fuel by the petroleum companies in Denmark.
6.8 Additives found in the environment
Concern for the impact of fuel additives upon the soil and groundwater environment has been described in particular for alkyl leads, MMT and MTBE. The number of studies on the environmental properties of other fuel additives is limited considering also the large number of additive compounds and the high volumes used. Still, important lessons can be learned from the alkyl lead, MMT and MTBE studies.
6.8.1 Alkyl lead and MMT It is well known that the air and soil in urban areas and close to heavily trafficked roads was impacted with lead from car combustion. Concern was expressed whether the ac-ceptable lead pressure on urban populations was exceeded and subsequently, require-ments for decreasing leading was enforced leading finally to a ban in 1996 in the US and in 2000 in the EU, se also section 6.4. In the years prior to the EU ban, some voices were raised from the motor and fuel industries cautioning that engine damages could re-sult from using unleaded gasoline, whereas other representatives of the industries were
29
confident that construction changes and alternative additives would remedy the effects of excluding lead from the gasoline /74/.
One alternative antiknock additive, methylcyclopentadienyl manganese tricarbonyl (MMT) was used in the US in combination with alkyl leads during the years 1958-1985 and in both unleaded and leaded gasoline in Canada since 1976 /74;75/. MMT is not widely used in Europe /76/, but the additive has been marketed in the United Kingdom /74/.
The use of MMT has been controversial in both the US and Canada in part due to al-leged damages to engines and catalysts, in part to concerns for environmental and hu-man health effects /77/. Trade of MMT has been restricted in Canada in 1997, the re-striction lifted in 1998 after legal disputes, and the use of MMT is now allowed in the US, although the actual use is very limited (<0.02% of US petrol in 1998, /74/).
A recent study implied that the use of MMT could be one of the reasons for increased manganese levels in the umbilical cord of neonates in Montreal compared to Paris, as well as for increased blood concentrations of manganese in urban areas with higher traf-fic density and higher airborne manganese levels than in suburban and small community areas, /78/ and references quoted herein. On the other hand, the level of lead was higher in cords and maternal blood in Paris (at the time of the study using leaded gasoline) than in Montreal (using MMT as gasoline antiknock additive). Manganese is an essential nu-trient for man but also a neurotoxin at too high concentrations.
A study on the environmental fate of MMT /79/ has shown rapid degradation catalyzed by light, slow or absent hydrolysis in the dark and an indication of binding to soil parti-cles comparable to that of the less mobile, dominating fuel plume constitutents, com-pare section 11.1.6. Using reported MMT concentrations in gasoline of 18 mg/L /75/ and water solubility of 0.029 g/L /79/ to provide an upper limit of the concentration in groundwater after a spill, see section 11 for the procedure, this can be estimated to 0.1-1 µg/L.
The lesson here is that using an element such as lead or manganese of potential human health and/or environmental concern as fuel additive should be considered carefully. Emission with exhaust can not be avoided and the potential impact upon air and soil quality will be challenged.
6.8.2 MTBE and alternative oxygenates The oxygenate methyl-tert-butylether (MTBE) was accepted for use in the US in 1979 as antiknock alternative to alkyl leads and as oxygenate for improved combustion giv-ing reduced exhaust concentration of carbon monoxide, benzene and 1,3-butadiene, and reduced air pollution with ozone /80/. Following the widespread detection of MTBE in groundwater after leakages of underground storage tanks, the use of MTBE is now banned in 15 states in the US and 5 more states are on their way with a ban /66/. In Europe, MTBE is primarily used as an antiknock additive with an annual consumption in the EU of 2 million tons (1996-1997) /81/. In Denmark, MTBE is not used in 92 and 95 octane gasoline (since May 1st 2001) by voluntary agreement between the petroleum companies and the Danish Environmental Protection Agency (EPA), and only minor amounts are used in 98 octane gasoline /82/.
30
It has been concluded that MTBE is not of concern for human health via environmental exposure /83/, indications of animal carcinogenic effects have been reported at high ex-posures /84/, but MTBE is not considered a human carcinogen /83/. Maximum con-taminant limits in groundwater and drinking water are consequently mainly based upon the unpleasant taste and odor of the compound.
Alternative oxygenates such as ETBE, TAME and ethanol are now being introduced to substitute MTBE /65/ and the technical requirements for their production discussed /85/. Still, as the other alkyl ethers have similar properties to those of MTBE, Table 6.5, the substitution is not likely to give the desired reduction in groundwater contamination in-cidents with oxygenates.
Oxygenate Water
solubility
Water solu-
bility from
gasoline
Log Kow Biodegradability
mg/L mg/L Aerobic Anaerobic
MTBE 50000 6000 1 Very slow Very slow
ETBE 10000 3000 2 Very slow Very slow
TAME 10000 2000 2 Very slow Very slow
DIPE 2000 - 2 Very slow Very slow
TBA Miscible 50000 0 Very slow Very slow
Ethanol Miscible 25000 0 Fast Fast
Table 6.5 Ranges of physical-chemical properties and biodegradability of selected oxygenates, from /86/.
Anaerobic degradation in aquifer slurries has been reported to 7-18 mg C/day for etha-nol, methanol and 2-propanol, while a degradation of the ethers MTBE, ETBE and TAME could not be detected /87/. In accordance with this, a study showed complete removal of ethanol from the groundwater in a controlled gasoline spill containing both ethanol and MTBE within 3 months, whereas MTBE spilled in the same amounts per-sisted for more than 6 months at concentrations higher than 125 mg/L /88/.
Probably due to the varying requirements among US states and counties, oxygenates such as TAME, DIPE and ETBE have been found at contaminated sites in Nebraska where only MTBE should have been added to the gasoline /89/, and the 87 octane gaso-line in Maine not subject to a regulatory requirement for addition of oxygenates was found to contain up to 15% MTBE and up to 8% TAME /66/. In a summary of the con-taminants found at leaking underground fuel tanks (LUFTs) in California, MTBE was found in 83% of 850 sites, TBA (degradation product of MTBE and used as oxygenate) in 61%, DIPE in 24%, ETB in 8.9% and TAME in 18% of the sites /90/.
The lesson here, see also section 6.4, is that use of compounds with high water solubil-ity and slow biodegradation as additives will imply risk of high concentration ground-water contamination.
6.8.3 Other fuel additives As said previously, the investigations on fuels additives in the environment have previ-ously mainly emphasized oxygenates (mainly MTBE) and occasionally lead scavengers in groundwater, and the metal antiknock additives alkyl leads and MMT in air and soil. Still, other additives may be found in e.g.: groundwater.
31
The US EPA holds a database for sites with ongoing remediation of MTBE contamina-tion /91/. Of the 367 sites with ongoing groundwater remediation for MTBE, the chlo-rinated compounds 1,1-dichloroethene, 1,2-dichloroethene, trichloroethene and penta-chloroethane were found in groundwater each at 3-5 sites, and the polar organic compounds ethanol and acetone at 3-5 sites as well.
Furthermore, studies of polar fuel constituents have demonstrated the presence of a range of such compounds in water extracts of fuels: ethanol, 2-propanol, 1-butanol, iso-butanol, 2-butanol, 2-butanone and 2-pentanone /92/. Furthermore, a series of phenols and aromatic amines were found in water extracts from gasoline, see Table 6.6.
Compound Detection frequency
in products
Maximum
concentration in
gasoline
Maximum
concentration in
water extract
(%) (mg/L) (mg/L)
Aniline 82 16 3.8
m-/p-Toluidines 82 28 2.2
o-Toluidine 77 18 1.4
Dimethylanilines 52 12 0.41
Phenol 80 130 0.51
m-/p-cresols 82 91 8.8
o-Cresol 82 99 6.6
Dimethylphenols 72 30 1.3
Table 6.6 Maximum concentrations of phenols and aromatic amines in gasoline and water extracts in a
study of 65 products /93/.
The data show that these polar compounds were found in most fuels at concentrations up to 10-100 mg/L gasoline, but it can not be established whether the origin is the petro-leum or the use of additives. In water extracts, the maximum concentrations were in the range 0.5-10 mg/L. These compounds would not be found with the analytical programs generally applied in investigations on fuel spills.
The lesson here is that identified polar water soluble fuel components may end up in groundwater to high concentrations (mg/L), but that detection of the compounds is not to be expected in routine investigations.
32
7 DATA ON DANISH ADDITIVE CONSUMPTION FROM OPEN SOURCES
Statistics Denmark maintain statistics on Danish import, production, consumption and export of goods, but the structure of the data did not allow for retrieving information on Danish import use of fuel additives (the use category was not a valid entry) or of spe-cific, known additives (a few compounds could be found as registered goods but were bundled with other compounds in product groups in the data base).
The Danish Product Register (PR) does not allow for open retrieval of data on com-pounds or products based upon use category and does not give used amounts for identi-fied additives. Therefore, a data retrieval was conducted in the PR by the AT for the DEPA and made available to the project. The keys used were the Danish use categories B6000, fuel additives, B6010, antiknock agents and B6020, other fuel additives. Sup-plementary, additives used in the Nordic countries were retrieved with the use category (UC62) A28, fuel additives.
The Internordic product database SPIN allows for open retrieval of data based upon use and industrial categories. With the limitations described in sections 4.3 and 4.4, infor-mation on dangerous additive products and compounds produced in or imported to Denmark was therefore mainly retrieved from the SPIN database. The use categories and industrial area codes applied in the information retrieval are summarized in Table 7.1. The Danish use category codes B6010 (anti-knocking agents) and B6050 (deposit inhibitors) can not be used as keys in SPIN.
Danish codes Swedish codes EU codes (UC 62)
Use category B6000 Fuel additives B6020 Other fuel additives
301 Fuel additives 302 Antiknock agents
A28 Fuel additives
Industrial category DF232000 Manufacture of re-fined petroleum prod-ucts
None None
Table 7.1 Use categories and industrial area codes used in retrieval of Danish consumption of additives
etc. in 2001 from the SPIN database.
The information on compounds imported to Denmark from the specified categories, Table 7.1, is summarized in Table 7.2. In the table, compounds noted with 0 t use in 2001 are registered for the use specified but no use was registered in 2001 in Denmark. Compounds noted with a – are without Danish registration for the specified purpose.
In the table, all additives that are simple petroleum fractions or products have been ex-cluded.
33
A large consumption in other Nordic countries of a few compounds with no use in Denmark should be noted:
• Methanol, 205 t in 2001 in Norway
• 2-Butanone 15 t in 2000 in Sweden
• Siloxanes, 47 t in 2001 in Norway
• Ethene vinylacetate polymers, 434 t in 2000 in Sweden.
These compounds should be considered potential additive compounds in Denmark as well.
The uncertainty associated with the information retrieval from the SPIN database can be illustrated with a few examples.
• MTBE is known to be added to 98 octane gasoline in Denmark but was not identi-fied as a fuel additive with use in Denmark in 2001 with the described retrieval pro-file.
• The compound 2-propanol has a use of 14 t as fuel additive in Denmark in 2001, but totally a use of 19,000 t for all purposes. Here, parts of the total consumption may be as fuel additive without being registered for that use but conversely, parts of the amount registered for use in fuel may be used for other fuels that gasoline and die-sel.
• The compound 2-ethylhexyl nitrate is the most commonly used cetane improver in Denmark with an estimated product concentration of 0.1 % in diesel, see section 6.2. With the reported consumption of diesel in Denmark in 2003 of 2,425,000 m3 /28/ and an estimated diesel density of 0.8 t/m3, the annual Danish use should be 1,900 t against the recorded 2001 use of 1,500 t.
Overall, the retrieved data can be considered to give part of the picture of Danish fuel additive consumption, but not the full picture.
The annual Danish consumption of gasoline and gas oil was in 2001 approximately 2,000,000 t and 2,500,000 t, respectively. Accordingly, an annual use of 2,000 t of an additive in one product as sold by all suppliers in Denmark would imply a product con-centration of that additive of 0.1 %. A use of 2 t would imply a product concentration of 1 ppm.
34
The dominating fuel additives (above approximately 100 t/year) used in Denmark in 2001 as registered in the Product Register as accessible from the SPIN database were:
• Fatty acids 3,237 t
• 2-Ethylhexylnitrate 1,501 t
• 2-Ethylhexanol 912 t
• A succinimide 508 t
• Maleic acid tridecylamide 268 t
• 2,6-bis(1,1-Dimethylethyl)phenol 133 t
• Triethanolamine 99 t
35
CAS no. Compound name Fuel additives and
other fuel addi-
tives
Manufacturing of
refined petroleum
products
50 00 0 Formaldehyde 011
0
57 55 6 1,2-Propanediol - 0
64 17 5 Ethanol - 0.2
67 56 1 Methanol - 1.8
67 63 0 2-Propanol 15 14
75 21 8 Ethylene oxide 0 0
75 56 9 Propylene oxide 0 0
94 91 7 2,2'-[(1-Methyl-1,2-ethanediyl)bis(nitrilomethylidyne)]bis-phenol 0 -
102 71 6 Triethanolamine - 99
104 76 7 2-Ethyl-1-hexanol 440 472
106 89 8 Epichlorohydrin - 0
107 98 2 Propylene glycol monomethyl ether - 0.9
110 16 7 Maleic acid - 0.5
110 25 8 (Z)-N-methyl-N-(1-oxo-9-octadecenyl)glycine (Oleoyl sarcosine) 0.0112
-
110 91 8 Morpholine 0.0213
-
111 42 2 Diethanolamine - 6.1
111 76 2 2-Butoxy ethanol - 29
112 57 2 Tetraethylenepentamine - 0.3
112 80 1 9-Octadecencarbocylic acid (Oleic acid) - 0.7
115 11 7 2-Methyl-1-propene (iso-Butylene) 0 -
128 37 0 2,6-bis(1,1-Dimethylethyl)-4-methylphenol (2,6-Di-tert-butyl-p-cresol) - 0.1
128 39 2 2,6-bis(1,1-Dimethylethyl)phenol 133 -
872 50 4 1-Methyl-2-pyrrolidinone - 0.1
2682 20 4 2-Methyl-4-iso-thiazolin-3-one (2-Methyl-3(2H)-isotiazolone) - 0
9003 29 6 Butene, homopolymer 3 -
25068 38 6 Epon 1001 Resin (4,4’-(1-Methylethylidene)-bis-phenol polymer with chlormethy- - 9.6
11 Registered as fuel additive, antiknock agent or used for fuel production 12 Registered as fuel additive, antiknock agent or used for fuel production, maximum annual use 1992-2002 13 Registered as fuel additive, antiknock agent or used for fuel production, maximum annual use 2000-2002
36
CAS no. Compound name Fuel additives and
other fuel addi-
tives
Manufacturing of
refined petroleum
products
loxiran, Bisphenol A epichlorhydrin copolymer))
26172 55 4 5-Chloro-2-methyl-4-isothiazolin-3-one (5-Chloro-2-methyl-3(2H)-isotiazolon) - 0
27193 86 8 Dodecylphenol 0 -
27247 96 7 2-Ethylhexyl nitrate 1501 -
29385 43 1 Tolyltriazole (Methyl-1H-benzotriazole) 0 -
36484 54 5 Bisphenol-A reacted with propyleneoxide or chloropropyleneoxide 0 -
53040 75 8 Dodecylphenolpoly(methyl)ethoxylate 1 -
61788 89 4 Fatty acids, C18-unsatd., dimers 0 -
61790 12 3 Tall oil fatty acids - 3237
63428 91 1 Formaldehyd reacted with 4-(1,1-dimethylpropyl)phenol, propyleneoxide and ethyl-eneoxide
0 -
68123 18 2 Bisphenol-A reacted with ethyleneoxide, propyleneoxide or chloropropyleneoxide 53 -
68439 80 5 Polyethylenpolyamines reacted with polybutenyl succinic anhydride 0 -
68891 84 1 1,2-Ethanediamine, reaction products with chlorinated isobutylene homopolymer 0.2214
-
84583 68 6 (Z)-4-Oxo-4-(tridecylamino)-2-butenoic acid (Maleic acid tridecylamide) 7 261
84605 20 9 Polyethylenpolyamines reacted with polyisobutenyl succinic anhydride 508 -
Table 7.2 The use of compounds in the categories specified in Table 7.1 in Denmark 2001 (tones per year) as retrieved from the SPIN database.
14 Registered as fuel additive, antiknock agent or used for fuel production, maximum annual use 1995-2002.
37
It should be noted from Table 7.2 that 14 compounds have been registered for use in fuel production or as fuel additives without a realized use in 2001. Whether this is because the compounds were used previously and abandoned before 2001 or because reporting of use amounts is not complete, can not be established.
In addition to the compounds listed in Table 7.2, a small number of inorganic compounds have been registered with use for fuel production: ammonia (0.02 t), aluminum oxide (12 t), titanium dioxide (8.8 t), molybdenum oxide (1.8 t), cobalt oxide (0.4 t), silica (0.1 t) and magnesium nitrate and chloride (both registered but without reported 2001 use). Whether these compounds are added to or used in processes producing the fuel can not be deduced from the information available here.
In order to cross check the data retrieval with use categories and industrial area codes, the Danish 2001 total use data for the potential additives identi-fied in chapter 6 were retrieved using the CAS numbers as key, see Appendix B. In the table of Appendix B, the compounds identified as used in Denmark as fuel additives or for fuel production has been included as well. The used amounts as found in the SPIN database are given, and the CAS numbers and names have been cross checked with the PR.
The table in Appendix B contains 235 compounds including both potential additives and compounds used as fuel additives and for fuel production. Of these 235 compounds, 82 were known to be used in Denmark in 2001 from the SPIN data base, 40 were registered for use for fuel purposes and 25 had a registered use for fuel purposes. For 18 compounds, the information on use and used amounts is confidential.
The compound list does not allow for identification of additional compounds actually used as fuel additives or for better estimation of the used amounts, simply because the additional information is not registered, accessible or up-dated.
38
8 RISK STRUCTURAL GROUPS AND PROPERTIES OF POTENTIAL ADDITIVES
In order to identify the additive compounds and structural groups that could potentially be of risk for soil, air and groundwater, a crude risk survey was conducted based upon the open source information on potential additives. The identification of structural groups potentially associated with a risk was based upon additive compounds potentially of risk with these groups, fol-lowed by an evaluation of the properties and groups trickering the risk. The risk groups should thus not be interpreted as functional groups that will al-ways imply risk but rather as warnings that with these functional groups pre-sent in additive compounds, special caution should be excersized to make sure that the additives are not associated with risk.
8.1 Classification
The risks for human health and the environment for the compounds identi-fied as potential fuel additives were compiled in the form of the registered classifications found in the Danish Product Register (PR) and given in the ta-ble of Appendix B. It should be recalled, that the classifications are primarily as submitted as part of the registration, see section 4.3. The health classifica-tions harmful, Xn, and irritant, Xi, may in most cases be considered less im-portant for low concentrations as expected for fuel additives.
A summary of the human health and environmental hazard classifications of the potential fuel additives is shown in Table 8.1. Note that some compounds may carry more than one classification.
Classification Tx
15 T
16 Xn
17 Xi
18 C
19 N
20
Number of registrations 5 17 16 17 11 15
Table 8.1 Summary of classifications of potential fuel additives with respect to human health or environmental hazard as registered in the Danish Product Register.
In order to identify groups of compounds that may be of risk for human health or the environment, the potential additives were subdivided after clas-sifications and after structural groups, and groups with one or more represen-tative with the classifications Tx, T or N were identified, see Table 8.2.
15 Tx: very toxic 16 T: toxic 17 Xn: harmful 18 Xi: irritant 19 C: corrosive 20 N: very environmentally harmful
39
Particular human health risk Very environmentally hazardous
Alkyl leads Alkyl leads
Metal carbonyls Amines
Amines Metal carbonyls
Alkyl nitrates Quaternary ammonium compounds
Alcohols and phenols Short chain halogenated alkanes
Short chain halogenated alkanes Heterocyclic compounds
Phthalates Peroxides
Table 8.2 Structural groups of potential fuel additives with one or more compound classified as of particular risk for human health (T, Tx) and/or the environment (N).
Compounds belonging to the structural types given in Table 8.2 should be given special attention in evaluating additives used or suggested for future use. It should be noted though that the conclusion is based upon a limited number of potential additives registered with classifications. Furthermore, it should be noted that not all compounds exhibiting one of the structural groups would be associated with risk. A case by case evaluation therefore is required.
Information on persistence and degradability was not included for the poten-tial additives because of the limited number of data reports on these proper-ties for most of the compounds.
8.2 Distribution
In order to assess the distribution of the potential risk additives to soil, air and groundwater, the phase distribution was estimated using a simple distri-bution model. The required data on physical-chemical properties were com-piled from open sources and both experimental and modelled /94-97/, see Appendix C.
Initially, structural groups with risk physical-chemical properties were ex-tracted from the potential additives with the required physical-chemical properties available from the specified sources, and groups with one or more representative with the risk properties were identified Table 8.3. All physi-cal-chemical data used are given in Appendix C. Risk physical-chemical properties were set arbitrarily to reflect low retardation, high water solubility and high tendency to evaporate from water to air.
Compounds belonging to the structural types given in Table 8.3 should be given special attention in evaluating additives used or suggested for future use. It should be noted though that the conclusion is based upon a limited number of potential additives with the required physical-chemical data avail-able. Furthermore, it should be noted that not all compounds exhibiting one of the structural groups would be associated with risk. A case by case evalua-tion therefore is required.
40
log Kow21 < 2 S22 > 10 g/L or miscible H23 > 0,1
Organic acids and their salts Organic acids and their salts Short chain ethers
Short chain alcohols and gly-cols
Short chain alcohols and gly-cols
Alkyl carbonates
Alcohol amines Alcohol amines Alkyl nitrates
Short chain aldehydes and ketones
Short chain aldehydes and ketones
Short chain alkenes
Short chain ethers Short chain ethers Siloxanes
Heterocyclic compounds Heterocyclic compounds
Alkyl carbonates Alkyl carbonates
Urea Urea
Phenol
Table 8.3 Structural groups of potential fuel additives with compounds of particular risk for evaporation to air and/or leaching to groundwater as defined in the headings.
Special attention should be given to structural types identified as of potential hazard, Table 8.2, and with risk physical-chemical properties, Table 8.3: al-cohols and phenols, heterocyclic compounds and alkyl nitrates, while still keeping in mind that not all representatives will be associated with risk.
The distribution of the potential fuel additives between soil, air and water was assessed with modelling according to a simple distribution model, see Appendix D, in principle based upon the distribution model used in risk as-sessment of contaminated sites in Denmark /97;98/.
The distribution modelling was based upon a subsoil with a low content of organic matter (0.1%), and a risk was assigned to potential additives with more than 10% distribution into mobile phases. This approach is considered realistic but precautionary. The distribution based upon a topsoil with higher content of organic matter (2%, less precautionary) is given in Appendix D as well.
The structural groups with risk of distribution into mobile phases (air and water) were identified as those groups with one or more representative with the risk properties as summarized in Table 8.4.
It should be noted that the distribution calculations do not consider the inter-actions with other constituents of the fuels and not the concentrations of the potential fuel additives, as the specific information required for these was not available at this stage of the project. It should further be noted, that the con-clusion is based upon a limited number of potential additives with the re-quired physical-chemical data available. Finally, it should be noted that not all compounds exhibiting one of the structural groups would be associated with risk. A case by case evaluation therefore is required.
21 Kow: partitioning coefficient octanol water 22 S: water solubility 23 H: Henry’s law constant
41
Risk for groundwater with > 10% distribu-
tion into water
Risk for air or indoor air with > 10% distri-
bution into air
Organic acids and their salts Short chain ethers
Short chain alcohols and glycols Short chain alkenes
Alcohol amines Siloxanes
Short chain aldehydes and ketones
Short chain ethers
Heterocyclic compounds
Alkyl carbonates
Urea
Table 8.4 Structural groups of potential fuel additives with compounds of risk for distribution into mobile phases as defined in the headings.
The main conclusion from evaluating the general properties of compounds used or suggested for use as fuel additives is thus that combinations of risk physical-chemical properties and hazard classifications may require further evaluation before use as a fuel additive.
8.3 Open source based risk survey
Among the potential 235 potential additives, 66 had registered classification of human health or environmental risks, and 29 were classified as of particu-lar risk. The risk compounds were primarily polar compounds, metalorganic compounds and a few apolar compounds (phthalates and chloroalkanes).
Among the 65 potential fuel additives with modelled distribution between water, air and soil, 49 were polar compounds with more than 10% distributed into water, whereas only 8 were volatile with more than 10% distributed into air.
In other words, a large fraction of the potential fuel additives would be ex-pected to constitute a risk for groundwater as polar, water soluble com-pounds, whereas the number of compounds that are expected to constitute a risk for air and indoor air is limited.
42
9 DATA ON ADDITIVES USED BY DANISH PETROLEUM COMPANIES
With the safety data sheets accompanying all products with hazardous com-pounds and the requirement for registration of hazardous compounds and their products, see chapter 4, information on the additive products and com-ponents used in Denmark is to some degree accessible from the petroleum companies. Furthermore, the companies have information on the amounts and concentrations of the additive products used in the fuel products.
In order to utilize this information in assessment of the risk for soil, air and groundwater associated with the use of gasoline and diesel additives, agree-ments were entered with the 5 major, Danish petroleum companies, see chap-ter 5, on access to this information. As the information is proprietary and as-sociated with considerable economical interests, the information was supplied under confidentiality, see Appendix E for example of confidentiality agreement. The main point of the confidentiality agreement was, that the companies would make information on their use of additive products avail-able in the form of safety data sheets and concentrations used in different fuel products (gasoline and diesel only) for a risk screening. Only informa-tion on additives associated with risk would subsequently be made openly accessible.
The requirement for confidentiality can be understood considering that the total Danish gasoline market in 2003 was 2.6 million m3, see chapter 5, with an estimated gross contribution to the companies of 2.5 billion DKR (assum-ing a gross contribution of 1 DKR/L gasoline /99/). Furthermore, with an an-nual use of additives for fuel of no less than 7000 t (see Table 7.2) and as-suming that the cost of additives are in the range between cost of the fuel ab refinery (1.5 DKR/L) and the cost ab station (10 DKR/L), the Danish addi-tive market may be assessed to between 15 and 90 million DKR.
Due to the requirement for confidentiality and the proprietary nature of the information obtained for the risk screening of additives to gasoline and die-sel, information on fuel products, additives products and additive concentra-tions used by the companies are not given in this section. Information on po-tential risk additives are supplied in section 11.2. In this chapter, anonymous information is presented to elucidate the general pattern of additive consump-tion.
The number of additive products and products used are summarized in Table 9.1 for the 5 major Danish companies.
The total number of additive products used and declared was 39, with totally 11 suppliers of additive products. Five additive producers supplied 34 of the products. Only 2 products were used by more than one petroleum company in the exact same form.
43
Company number A B C D E
Number of fuel suppliers used
1 1 4 3 3
Number of additive pro-ducts used
9 7 5 3 17
Number of additive pro-ducers used
4 4 3 3 7
Table 9.1 Fuel suppliers, additive products and producers as used by the five major Danish petroleum companies for gasoline and diesel.
It should be noted here, that additives are added at the refinery and at depots, see chapter 6. Therefore, companies with own refineries will be able to de-clare all additives used in their products, whereas companies buying the fuel products on the open market can only declare the performance additives added on their depots and further refer to their suppliers for information on additives used at the refineries. It is assessed, that this compilation of addi-tives used covers 35-40% of the Danish market completely, 30-35% of the market well, 10-20% of the market potentially with missing refinery addi-tives and 5-15% without any information. An overall coverage of at the least 70% of the refinery additives and 85% of the performance additives is esti-mated.
In assessing the properties of the additives identified as available from the safety data sheets, it was emphasized that as only hazardous compounds above defined concentrations limits must be declared, see chapter 4, a full description of the composition of the additives used would not be obtained. For the 5 major additive suppliers, 1-2 compounds were not identified per product (totally 34 products) and for most products, it could not be excluded that compounds were not declared (declared compounds amounted to less than 100% of contents).
44
10 DATA ON USED ADDITIVES FROM ADDITIVE PRODUCERS
In order to retrieve the information on additive compounds not declared in the safety data sheets handed over by the petroleum companies, the additive producers were approached through the Health Safety and Legislation sub-committee (HSL) of the Technical Committee of Petroleum Additive Manu-facturers in Europe (ATC). The five HSL members identified as major sup-pliers to Danish petroleum companies agreed to provide additional informa-tion on their products for use in the risk screening under confidentiality agreements similar to those entered with the Danish Petroleum companies, see Appendix F.
The cooperation followed the flow showed in Figure 10.1.
Figure 10.1 Flow in cooperation between additive producers and DHI as project organization.
For each additive product identified as used in Denmark, the missing infor-mation included:
• Chemical identity of additive compounds that could not be identified un-equivocally from the safety data sheet declaration
• The chemical identity of any additive compounds not declared in the safety data sheets
For each compound, additional information on the properties was asked for, based upon information already compiled from open sources:
• Acid dissociation constant, pKa, if relevant
List of missing data to producers
Missing data to DHI
Preliminary list of risk additives to producers
Comments and additional data to DHI
Draft report to producers
Comments to DHI
Option for additional data from producers
Report with temporary list of risk additives
Publication of final list of risk additives
45
• Partitioning coefficient octanol water, log Kow
• Vapor pressure, P
• Water solubility, S
• Anaerobic and aerobic degradability.
Classification of human health and environmental risk in accordance with /17/ as implemented in /15/ and subsequently, when relevant molecular weight (for polymers).
It should be noted, that the complete datasets and calculations (in the form of spread sheets) and a description of the risk screening procedure (section 11) have been shared with the additive producers for commenting, verification and correcting.
Totally 34 additive products were identified as delivered from the 5 major suppliers to the Danish petroleum companies for use in gasoline and diesel. The level of information obtained is shown in Table 10.1.
Due to the requirement for confidentiality and the proprietary nature of the information obtained for the risk screening of additives to gasoline and die-sel, information on additives products and additive concentrations supplied by the companies is not given in this section. Information on potential risk additives is supplied in section 11.2. In this chapter, anonymous information is presented to elucidate the general pattern of additive consumption.
A B C D E
Number of products 8 4 7 10 5
Mean missing data points per product SDS
24 initially
1.9 4.3 1.3 3.0 2.4
Additive compounds without identification in final screen-ing
9 2 0 9 1
Additive compounds with missing data in final screen-ing
1 0 0 7 1
Table 10.1 Development in information level for the additive products from the 5 major sup-pliers to the Danish market in the project.
The term “missing data points” signifies compounds that were not identified in the SDS. The unidentified compounds and compounds without data from company D were mainly compounds purchased from subsuppliers.
It should be noted, that the suppliers and producers of “after market” addi-tives have not been included. Furthermore, one additive producer initially in-
24 SDS: safety data sheet
46
dicated to supply the Danish market but did not subsequently submit infor-mation on additive products and compounds delivered.
47
48
11 RISK SCREENING
Screening for potential risk additives was done as a filtering process remov-ing those compounds that with high probability will be of no added risk (compared to the inherent gasoline or diesel constituents) after a spill. In other words, the process was not a risk assessment and not an identification of risk compounds, but rather a removal from future investigations programs for fuel spills of those compounds that are probably not risk compounds. The end points considered were soil, air and groundwater, and thresholds were based upon Danish maximum contaminant concentrations.
It should be noted that the filtering process is only valid for additives spilled with fuel, because the basic principle in the risk screening was to identify those additives that would cause added risk compared to the risk associated with and accepted for the use of petroleum based fuels. It should further be emphasized that the risk screening does not include any potential metabolites of additives.
11.1 Risk screening method
The risk addressed with the screening are described in Figure 11.1.
Note: Upper left. Risks addressed are for direct exposure to soil, for exposure to air and in-door air and to groundwater. Upper right. The screening addresses compounds (red plume) that may be transported faster than mobile fuel components (solid black line). Lower left. In-cluded are also compounds (red plume) that may be left after degradation of degradable fuel components (solid black line, after plume retraction). Lower right. The effects of compounds (red plume) that may inhibit degradation of fuel components (extended solid black line) and thus increase their transport are not included.
Figure 11.1 Risks addressed in the screening.
Example: 2-EthylhexylnitrateExample: 2-Ethylhexylnitrate
Example: MTBEExample: MTBE
Soil/air
Air/indoor air
Groundwater
Soil/air
Air/indoor air
Groundwater
Example: ethanolExample: ethanolExample: 2-EthylhexylnitrateExample: 2-Ethylhexylnitrate
Example: MTBEExample: MTBE
Soil/air
Air/indoor air
Groundwater
Soil/air
Air/indoor air
Groundwater
Example: ethanolExample: ethanol
49
The steps in the applied screening method are described in details in the sub-sequent sections.
11.1.1 Thresholds for human toxicity or environmental hazard
In Denmark, the official groundwater protection strategy is based upon the principle that all resources (aquifers) should be uncontaminated. Therefore, even a compound without recognized human health effects or environmental hazard will be considered a threat to the groundwater resource if introduced through contamination, but the protection level will be higher (maximum contaminant limits, MCL’s, lower) for compounds with identified ef-fects/hazards. Typical Danish groundwater criteria are in the range 0.1-10 µg/L, with typical air or soil air criteria in the range 10-6 – 0.5 mg/m3 /100/.
In Table 11.1, the thresholds applied in the filtering of additives in this pro-ject are given. The thresholds for toxic or very toxic (T or Tx) or very envi-ronmentally hazardous (N) compounds are set at the lowest level of Danish quality criteria. Similarly, the thresholds for compounds with lower classifi-cations are set at the highest level of criteria.
With no data on human health or environmental hazard, the lowest threshold values were applied. The risk phrases behind the classifications are shown in Table 11.2. The highest risk classification of a compound is applied, e.g.: ir-respective of how the concentration in products impacts classification.
Threshold
soil water
(µµµµg/L)
Threshold
soil air
(mg/m3)
Compounds classified as toxic or very toxic (T, Tx)
0.1 10-6
Compounds classified as very environmen-tally hazardous (N)
0.1 0.5
Compounds with data on both human health and environmental hazard and lower classifi-cations
10 0.5
Compounds without data on both human health and environmental hazard
0.1 10-6
Table 11.1 Threshold for additives in soil water and soil air based upon human health and environmental hazard criteria.
Irrespective of the generic threshold values in Table 11.1, a generic threshold is overruled by any Danish maximum contaminant concentration stated for air, soil air, groundwater or recipients.
50
Classification Risk phrase
number
Risk phrase text
R23 Toxic by inhalation
R24 Toxic in contact with skin
R25 Toxic if swallowed
R45 May cause cancer, Carc 1, Carc 2
R46 May cause heritable genetic damage, Mut 1, Mut 2
R48 Danger of serious damage to health by prolonged exposure
R49 May cause cancer by inhalation
R60 May impair fertility, Rep 1, Rep 2
T, toxic
R61 May cause harm to the unborn child, Rep 1, Rep 2
R26 Very toxic by inhalation
R27 Very toxic in contact with skin
R28 Very toxic if swallowed
Tx, very toxic
R39 Very toxic: danger of very serious irreversible effects through inhalation, in contact with skin and if swal-lowed
R50 Very toxic to aquatic organisms
R50 and Very toxic to aquatic organisms
R53 May cause long-term adverse effects in the aquatic environment
R51 and Toxic to aquatic organisms
R53 May cause long-term adverse effects in the aquatic environment
R54 Toxic to flora
R55 Toxic to fauna
R56 Toxic to soil organisms
R57 Toxic to bees
R58 May cause long-term adverse effects in the environ-ment
N, very envi-ronmentally hazardous
R59 Dangerous for the ozone layer
Table 11.2 Risk phrases behind the T, Tx and N classifications.
11.1.2 Filter for amounts and concentrations
Fuel spill amounts can vary from a few kg to several tons with the impact upon soil and groundwater depending upon the amount spilled. The associ-ated spill of additives depends upon both total fuel spill amount and the addi-tive concentration in the fuel.
Due to the variability of spilled additive amounts and to the fact that a larger amount will primarily give a larger volume affected, no filter has been esta-blished for amounts. The additive concentrations are included in the parti-tioning filter described later.
In calculation of the additive concentrations in Danish fuels, the highest dos-age of the additive product used in Danish fuels and the upper range limit for the concentration of the additive compound in the additive product were used. For practical reasons, fuel and additive densities of 1 g/mL were as-sumed but the error associated with this is considered minor compared to the overall uncertainties of the screening process.
51
In evaluation of monomers potentially present in additives containing poly-mers, 1‰ concentration of the monomers in the additive product was as-sumed, unless the producer provided specific information contradicting this.
11.1.3 Filter for inherent petroleum constituents Additives that are also inherent constituents of gasoline or diesel (without additives) were not considered to ad risk to the product, if the additive con-centrations are similar to that in the raw fuel.
Filter: Typical max. additive concentration of inherent fuel constituent be-low mean value for the fuel in question means, that the compound was considered without added risk.
The gasoline and diesel composition data used for reference were those com-piled for the Danish Environmental Agency /2/, including the data published by the American Petroleum Industry /3/. The composition data for mid range unleaded 95 octane gasoline and for diesel were used, respectively.
11.1.4 Filter for very volatile components with respect to risk at direct soil exposure No threshold was applied for compounds classified as toxic or very toxic with respect to direct soil exposure (ingestion, dermal exposure or inhala-tion). Still, if the compounds are more volatile than the most volatile inherent gasoline constituents of high human health classification, e.g.: benzene, va-por pressure 100 mm Hg or 13,000 Pa), the compounds would vaporize be-fore benzene from the soil and the presence of the additive would not add a risk to the product.
Filter: Vapour pressure above 13,000 Pa means that the compound was considered without added risk at direct soil exposure.
11.1.5 Filter for partitioning to soil air and soil water
The highest concentrations of additives in soil air and soil water will result from equilibrium between free phase fuel, soil air and soil water.
The highest concentration possible in soil water (Cmax, soil water, additive) depends upon the additive concentration (weight fraction, Xadditive) in the fuel (strictly speaking the molar fraction but this is not easily calculated for complex mix-tures such as fuels) and the water solubility (Sadditive) /2;101/:
Cmax, soil water, additive = Xadditive * Sadditive
The water solubility data used were at 20°C, unless otherwise stated.
Similarly, the highest concentration possible in soil air (Cmax, soil air, additive) de-pends upon the additive concentration (weight fraction, Xadditive) in the fuel (again strictly speaking the molar fraction), the vapour pressure (Padditive) and the molar weight of the additive (Madditive):
52
Cmax, soil air, additive = Xadditive * Padditivee*Madditive/RT
with T being the absolute temperature (here set to 20°C), and R the gas con-stant.
The vapor pressure data used were at 20°C, unless otherwise stated
Using these calculated values for maximum soil air and soil water concentra-tions as estimated maximum air and groundwater concentrations is consid-ered a precautious approach. Effects of dilution, retardation and degradation in the unsaturated zone are not considered. Also, the effects of the compli-cated matrices of fuels upon the partitioning of the additives (effects upon chemical potential in both fuel and water) are not considered.
Filter: The estimated highest soil air and soil water concentrations are evaluated against the threshold values given in Table 11.1. A con-centration below threshold means that the compound is considered without added risk.
11.1.6 Filter for aquifer retardation
Sorption of additives to aquifer sediments will retard transport of the com-pounds with the groundwater. A typical contaminant plume at a fuel con-taminated site will be dominated by mobile fuel components such as BTEX, other alkylbenzenes and MTBE. The sorption depends upon both sediment properties (in particular sedimentary organic carbon content) and compound properties (in particular partitioning constant water – soil organic matter). Comparison of partitioning coefficients is most conveniently done based upon the partitioning coefficient octanol/water where the data are readily available for most compounds. For the typical, dominating plume constitu-ents, the partitioning coefficients octanol/water (log Kow, typical, dominating) are < 4. Therefore, the partitioning coefficients of the additives (log Kow, additive) were evaluated against the log Kow, typical, dominating = 4.
If the additive partitioning coefficient is above 4, the additive will be trans-ported slower than the typical fuel plume constituents and the additive will thus not add to the groundwater risk of a fuel spill. In order to take into ac-count the risk of having a residual plume of additives left when the fuel plume retracts, the filter was only applied for additives that are aerobically biodegradable as are most typical fuel components.
Filter: log Kow, additive > 4 means that the compound is considered without added risk, if the additive is readily aerobically degradable.
11.1.7 Filter for aquifer degradation
Fast degradation of additives in the aquifer means fast removal of the com-pounds as groundwater contaminants and thus the elimination of a long term risk. Both aerobic and anaerobic conditions occur in aquifers and in order to
53
ensure removal by degradation, the additive must be readily biodegradable both aerobically and anaerobically. Many aerobically degradable compounds are degraded slowly anaerobically, in particular with the most reduced methanogenic conditions, and vice versa. Generally, a compound is consid-ered readily aerobically biodegradable if more than 60% is degraded within 28 days (OECD guidelines 301 definitions and conditions, 20°C laboratory test, or equivalent). Anaerobic biodegradability is mostly quantified in terms of a 1. order rate constant for degradation or a half life. The 60% degradation over 28 days resembles a 1. order rate constant, k1, additive, of 0,033 days-1 and a half life, t½, of 21 days.
If an additive is more mobile than typical fuel constituents, it may contami-nate groundwater ahead of the fuel plume even if it is biodegradable due to e.g.: fast groundwater transport or to low capacity for biodegradation in the aquifer. Therefore, the filter for biodegradability was only applied for addi-tives that are retarded more than typical fuel constituents.
It should be noted that data on anaerobic biodegradability are generally not given in chemical safety sheets or the data behind these sheets, and this part of the filter has therefore in reality removed only very few additives from the list of potential risk compounds. Also, it should be noted that as mentioned before, degradation products of additives were not considered with this ap-proach. The anaerobic biodegradation data were compiled in order to enable a subsequent evaluation of the risk associated with mobile but biodegradable additives.
Filter: Ready biodegradability aerobically (>60% over 28 days after OECD 301 or equivalent) and log Kow, additive > 4 means that the compound is considered without added risk.
11.1.8 Flow in filter process
The overall flow in the filter process is presented in Figure 11.2.
If a compound was filtered off as of no potential risk at one point in the screening, data for the subsequent points were not compiled.
54
No risk Filter or threshold Potential risk If yes, no risk ad-ded for soil, air and groundwater
⇐ Max. additive concentration be-low mean concentration of the same compound in fuel without additives
⇓
Classification as toxic or very toxic
⇓
Compound vaporize less than volatile, high risk fuel compo-nents
⇒ If yes, potential added soil risk
⇓
Selection of threshold from clas-sification T, Tx or N, alterna-tively choose Danish MCL
⇓
If yes, no added air risk
⇐ Highest soil air concentration at or below threshold
⇒ If no, potential added air risk
⇓
If yes, no added groundwater risk
⇐ Highest soil water concentration at or below threshold
⇓
Additive retarded more than mobile fuel components?
⇒ If no, potential added groundwater risk
⇓
If yes, no added groundwater risk
⇐ Readily biodegradable aerobi-cally
⇓
Remaining compounds ⇒ Potential added groundwater risk
Figure 11.2 Flow in filtering process removing additive compounds that will with high probabil-ity be of no added risk after a fuel spill.
11.1.9 Data compilation
Data on physical chemical properties were initially retrieved from open sources, Table 11.3. For some additives, no data were available from the open sources, and producer data were then used. Conservative values were selected, if ranges were offered.
55
Data source Priority Comments
Syracuse PhysProp Data-base /95/
1
ESIS /20/ 2 Highest values used
Chemfinder /102/ 3
EPIwin 3.11 /103/ 4 If estimated data were used, this is commented in the data evaluation
Producer data 5 If producer data were used, this is commented in the data evaluation
Table 11.3 Sources and data prioritization for physical chemical properties of additives.
If unambiguous structural data were not supplied, further structural data were sought in the STNeasy, an online chemical database /104/ including access to the major chemical database: Chemical Abstracts.
For organic acids or bases, log Kow, additive given in the open sources is gener-ally designated to the unionized form in correspondence with the convention used in EPIwin 3.11, unless otherwise stated in the source. The impact of ionization was set to a decrease of log Kow, additive with 4, based upon the ef-fect of ionization observed for carboxylic acids /105/. Correspondingly, the S values for organic acids and bases were increased by a factor 104 for the ion-ized form compared to the values listed in the open sources and designated to the unionized form. In case of experimentally based partitioning coefficients and water solubilities for ionized compounds, the experimental data were used directly and without correction for ionization, see Table 11.4 for sum-mary of approach. In accordance with the typical groundwater pH range of 4.5-8.5, all organic compounds with pKa below 8.5 or with pKb below 9.5 are considered ionizable.
For water miscible compounds, the water solubility is set to 1,000 g/L (~1 kg/L).
Partitioning coefficient
octanol/ water
Water solubility
Experimental partitioning coefficient and water solubility for ionized com-pound available
Experimental value used directly
Experimental value used directly
Experimental partitioning coefficient and water solubility for unionized compound available
Value corrected for ioni-zation
Value corrected for ioni-zation
Modelbased partitioning coefficient and water solubility available
Value corrected for ioni-zation
Value corrected for ioni-zation
Modelbased partitioning coefficient and experimental water solubility for ionized compound available
Value corrected for ioni-zation
Experimental value used directly
Table 11.4 Partitioning coefficients and water solubilities for ionizable compounds (pKa below 8.5 or pKb below 9.5).
Information on biodegradation was retrieved from ESIS (European chemical Substances Information System) /20/ with the lowest biodegradability for
56
groundwater used, if found, otherwise the lowest biodegradability found for other matrices reported was used.
The classifications for human health or environmental hazard were as given in the ESIS database /20/, from the lists published by the Danish Environ-mental Protection Agency (DEPA): the list of dangerous compounds and the self classification list, as found in the effect list /106/, and from the database over substances that have been discussed or are at present being discussed by the Commission Working Groups (CWG) on the Classification and Labelling for environmental effects (N-Class) /107/. Furthermore, classifications from the Danish Product Register were included. The highest classification for a substance was always applied. For some additives, no data were available from the open sources and producer classifications were used from safety data sheets or from additional information from the producers. In cases where the classification was not supported by data for one or more of the re-quired end points (classifications not complete), the precautionary principle was applied and risk assignments have been based upon T and N classifica-tion. In classification for human health hazards, data on dermal and oral tox-icity have been considered sufficient and data for toxicity by inhalation have not been requested. The sources and data prioritization is summarized in Table 11.5.
Data source Priority Comments
ESIS /20/ 1
DEPA effect list /106/ 2
Danish Product Register 3
N-Class /107/ 4 Used only to verify that revised classifications were not under consideration
Producer classifications 5 If safety data sheet classifications were used, this was commented in the data
Table 11.5 Sources and data prioritization for classifications of additives.
11.1.10 Analytical methods for monitoring and control
Most additives have properties that are different from those of petroleum de-rived fuel components with respect in particular to polarity (most groups) and molecular weight (polymers), see section 6.1. These differences in prop-erties between additives and other fuel components have the effect that many fuel additives will not be identified with the analytical methods used as stan-dard in investigations of fuel spills: analysis for fuel constituents and oxy-genates using liquid-liquid extraction (LLE) or purge and trap (P&T), gas chromatography (GC) and flame ionization (FID) or mass spectrometry (MS) identification/quantification. Accordingly, a qualitative assessment is given of the possibilities of analyzing the compounds in the relevant medium (air, water) as part of the evaluation of additive compounds suggested to add risk to the fuel products. In the assessment, a requirement for an analytical detec-
57
tion limit of 1/10 of the threshold or allowable maximum concentration is set in accordance with Danish guidelines /98/.
11.1.11 Testing and discussion of the screening method
The screening method was tested using four additives with different proper-ties: 1,2-dichloroethane (DCA, lead scavenger added previously to gasoline with alkyl leads), tetraethyl lead (TEL, antiknock agent added previously to gasoline), methyl-tert-butylether (MTBE, oxygenate added to gasoline) and 2-ethylhexylnitrate (2-EHN, cetane improver added to diesel). Open source information on additive concentrations and properties was used /33;38;94-97/.
The data used for testing are given in Table 11.6 with the risk assignment and its cause (-s). The test demonstrates that compounds with a known groundwater risk (DCA and MTBE) were identified as such. The two toxic or very toxic compounds DCA and TEL were of course classified with a soil risk, the two volatile compounds DCA and MTBE as expected with an air risk, but TEL was, slightly surprising, also classified as associated with po-tential air risk. Furthermore, 2-EHN was classified with both an air and a groundwater risk.
2-EHN is a good example of the sensitivity of the risk screening for the qual-ity of the data used. The compound was classified for a potential groundwa-ter risk with an estimated maximum concentration of 20 µg/L which is just above the generic threshold of 10 µg/L. The water solubility used in the risk screening was obtained using the modeling approach of EPIwin /103/ as 0.02 g/L. Alternative values would be 0.42 g/L /20/ giving an estimated maximum groundwater concentration of 420 µg/L or 0.013 g/L /108/ giving a ground-water concentration of 13 µg/L. These calculations were as stated above based upon estimated maximum additive concentrations in diesel as stated in an open source /30/, but with a lower product concentration and the lowest water solubility used in the calculations, the compound would not have been assigned a groundwater risk. Furthermore, it may be questioned whether a threshold or a MCL should at all be imposed for a compound that is not clas-sified for serious human health or environmental risks. Additionally, 2-EHN is hydrolyzed in aqueous solution yielding the corresponding alcohol and ni-trate /108/. This effect is not considered in the risk screening but would, if occurring at significant rate, have reduced the estimated maximum ground-water concentration. Still, the message from the risk screening is that this compound may occur in groundwater in high concentrations after a diesel spill.
Similarly, 2-EHN was classified for an air risk with the estimated maximum soil air concentration at 1.9 mg/m3 and thus close to but exceeding the threshold for compounds without serious human health classification of 0.5 mg/m3. The vapor pressure used was as declared by the producer association 27 Pa at 20°C /108/, but had a vapor pressure of 4.7 Pa /20/ as registered in the EU ESIS database been used, a maximum air concentration of 0.33 mg/m3 would have resulted and had a calculated vapor pressure of 35 pa
58
/103/ been used, the result would have been 2.5 mg/m3. Also, the air thresh-old used here was for compounds not classified as toxic or very toxic, be-cause no human health based risk classifications were found in the European database (EINECS, /20/). Still, open source information on 2-EHN /108/ classifies this compound as harmful by inhalation, a less serious human health classification that would not have triggered low thresholds in this screening. Here, it may be questioned whether it is acceptable to risk rather high soil air concentrations of a compound being harmful after inhalation. Still, the message from the risk screening is that this compound may occur in soil air and indoor air after a spill.
Conversely, 2-EHN was not classified for a soil risk because again, no hu-man health based risk classifications were found in the European database (EINECS, /20/). Still, the open source information on 2-EHN /108/ classifies this compound as harmful in contact with skin, again a less serious human health classification that would not have triggered a soil risk in this screen-ing. Here, it may be questioned whether it is acceptable to risk rather high re-sidual soil concentrations (the compound is considerably less volatile than the most harmful fuel components) of a compound being harmful after skin contact. Still, the message from the risk screening is that the added risk to soil caused by this compound as compared to the risk of the inherent fuel components is probably not important.
Overall, the risk screening is considered a conservative tool for filtering off compounds added to fuel that do not impose an added risk as compared to the inherent fuel components in case of spill.
59
Compo-
nent
name
CAS regi-
stry number
Concen-
tration in
product
pKa log
Kow
P S Degradability Classifi-
cation
Threshold/
calculated
air
Threshold/
calculated
groundwa-
ter
Risk as-
signment
g/L hPa
(20°
C)
g/L Aerobic Anaero-bic
mg/m3 µg/L
DCA 107-06-2 0.3 /38/ - 1.45 87 8.7 0%/21 days
<20%/4 months
T, R45 1*10-4
/102 1/2.6*10
3 Soil
Air Groundwa-ter
TEL 78-00-2 0.7 /38/ - 4.32 0.35 2*10-4
nd25
nd Tx, R61-26/27/28 N, R50/53
3*10-4
/3.3 0.1/0.1 Soil Air
MTBE 1634-04-4 150 /109/ - 0.94 270 50 50%/152 days
nr26
3*10-2
/ 1.5*10
5
5/7.5*106 Air
Groundwa-ter
2-EHN 27247-96-7 1.0 /30/ - 4.14 0.27 2*10-2
/96/ 0%/ 21 days
0%/ 21 days
nr 0.5/1.9 10/20 Groundwa-ter
Table 11.6 Risk assignment for known gasoline additives, test cases (open source data).
25 nd: no data available 26 nr: no relevant classification
60
11.2 Results of risk screening
The risk screening comprised 34 additive products with totally 95 additive compounds. For a number of additive compounds, an added risk for groundwater or air could not be excluded, see Table 11.7.
Please, note that three additional additives with a potential risk for groundwater were identified from open source information on additives used in Denmark, see section 12.3.
For each additive assigned a potential risk, the screening is further commented upon be-low. The additive compound key properties in the risk screening are listed for those ad-ditives in Appendix G. The methods used for calculation of concentrations in ground-water and soil air are described in section 11.1, and the data on additive compound concentrations in the fuel products are based upon dosages of additive products to petro-leum products are as declared by the petroleum companies and the concentrations of additive compounds in the additive products as declared by the additive producers.
61
Compound Number of
additive pro-
ducers/ pro-
ducts
Number of 5
Danish pe-
troleum
companies
using the
additive
Classifications for particu-
lar risk for human health
and/or the environment
Potential risk
Name CAS number Human health
Environmen-tal hazard
2-Propanol 67-63-0 1/2 3 -27
- Groundwater
2-Ethylhexyl nitrate 27247-96-7 5/6 5 - - Groundwater and soil air
2-Ethylhexan-1-ol 104-76-7 2/4 3 - N: R51/53 Groundwater
1,2-ethanediamine reaction products with chlorinated polyisobutylene
68891-84-9 1/1 1 - - (Groundwater)28
and (soil air)
1-Propene, 2-methyl-, ho-mopolymer, hydrofomyla-tion products,
337367-30-3 2/3 3 - - (Groundwater)
Polyalkylene polyamine nd29
1/1 1 - N: R51/53 Groundwater
Maleic acid tridecylamide 84583-68-6 1/2 2 - - (Groundwater)
Tetrapropenylbutanedioic acid
27859-58-1 1/1 1 - - (Groundwater)
1,2-bis(2-Ethylhexyloxycarbonyl) ethanesulphonate potas-sium salt
7491-09-0 1/3 2 - - Groundwater
Polyolefin Mannic base nd29
1/1 1 - - (Groundwater)
Table 11.7 Additive compounds that may cause added risk for air and/or groundwater.
27 -: no classification 28 (): the risk assignment is preliminary only and additional data are required 29 No CAS no. given 62
11.2.1 Classic additives The term “classic additives” is used to describe the group of additive compounds of one well defined structure and with both chemical-physical data and published human health and environmental risk classifications. Most of the fuel additives that have previously been considered with respect to risk for soil and groundwater protection belong to this group. Examples are tetraethyl lead, 1,2-dichloroethane and MTBE.
2-Propanol, CAS 67-63-0 The risk assignment for groundwater for the additive compound 2-propanol, structural formula in Figure 11.3, is based upon declared lower and upper limits of the dosage used for gasoline and diesel, and in addition on an upper and lower limit declared for the concentration of this compound in the two products in question. The expected and realistic maximum groundwater concentration would be 150 µg/L estimated from de-clared typical dosages and an spill estimate of 1000 L. The compound is without human health and environmental risk classifications that would add risk in case of a fuel spill. The compound is readily biodegradable both aerobically and anaerobically and would thus biodegrade in the aquifer after a spill. Still, the compound is very mobile and water soluble and could thus be transported with groundwater ahead of fuel based contami-nants, see Figure 11.1, upper right. The information available and methods applied here do not allow for evaluation of the risk of inhibition of fuel component degradation, see Figure 11.1, lower right, and not for assessing the estimated time for biodegradation in an aquifer.
Figure 11.3 Structural formula of 2-propanol.
It should be emphasized here, that with a maximum content of 5% of 2-propanol in the additive product and a maximum dosage of the product of 20 ppm, the highest concen-tration of 2-propanol in the fuel products would be 1 mg/L. A 1000 L fuel spill would thus release 1000 mg 2-propanol and the highest volume contaminated to the maximum concentration of 1000 µg/L would be 1 m3, Table 11.8.
The compound is not identified with the analytical programs generally used for groundwater after fuel spills, but analysis with the required limit of detection is possi-ble.
63
Matrix Threshold m3 contamina-
ted to thres-
hold30
Estimated ma-
ximum con-
centration
m3 contami-
nated to maxi-
mum concen-
tration
Groundwater 10 µg/L 100 1000 µg/L 1
Table 11.8 Estimated effects on soil air and groundwater after spill for 2-propanol.
It should be noted that the registered use in Denmark of 2-propanol as fuel additive and for fuel manufacturing was 29 t as compared to the total consumption of 19,000 t in 2001.
2-Ethylhexyl nitrate, CAS 27247-96-7 The risk assignment for groundwater and air for the additive compound 2-ethylhexyl ni-trate, structural formula in Figure 11.4, is based upon declared lower and upper limits of the dosage used for diesel. The expected and realistic maximum groundwater concentra-tion would be 13 µg/L and the expected and realistic maximum air concentration 1.9 mg/m3, both estimated from declared typical dosages. Please, note that the risk screen-ing here was done with additive concentrations and dosages, as well as physical-chemical data supplied by the additive producers as opposed to the example in Table 11.6 where only open source information was used. The compound may be without human health and environmental risk classifications that would add risk in case of a fuel spill, see the discussion in section 11.1.10. The safety data sheets made available for the project and the product characterization published by the additive producers /108/ agree that the compounds should be classified as harmful by inhalation (R20) and upon skin contact (R21) and is associated with risk for explo-sion if heated in confinement (R44). Two safety data sheets declare that the compound is toxic to aquatic organisms and may cause long term adverse effects in the aquatic en-vironment (R51/53), while the remaining three do not. The product characterization states that toxicity to aquatic organisms is so low (LC50/EC50 > 10mg/L), that the com-pound should not be classified with R51/53.
The compound is neither aerobically nor anaerobically readily biodegradable. Abiotic hydrolysis has been reported /108/, but the impact upon removal from groundwater can not be evaluated from the data available. It should be recalled that the hydrolysis prod-uct is 2-ethylhexanol, see below.
The compound is not biodegradable and not very mobile and water soluble and could thus remain in groundwater after degradation of the more degradable fuel based con-taminants, see Figure 11.1, lower left. The information available and methods applied here do not allow for assessing the estimated time for abiotic degradation in an aquifer.
With a maximum content of 100% of 2-ethylhexyl nitrate in the additive product and a maximum dosage of the product of 2‰, the highest concentration of 2-ethylhexyl ni-trate in the fuel products would be 2 g/L. A 1000 L fuel spill would thus release 2 kg 2-ethylhexyl nitrate and the highest volumes of air or water contaminated to the maximum concentrations 3.9 mg/m3 and 26 µg/L, respectively, would be 500,000 m3 air and 80,000 m3 groundwater, Table 11.9.
30 Threshold as defined in section 11.1.1
64
Figure 11.4 Structural formula for 2-ethylhexyl nitrate.
Matrix Threshold m3 contamina-
ted to thres-
hold
Estimated ma-
ximum con-
centration
m3 contami-
nated to maxi-
mum concen-
tration
Groundwater 10 µg/L 200,000 26 µg/L 77,000
Soil air 0.5 mg/m3 4,000,000 3.9 mg/m
3 510,000
Table 11.9 Estimated effects on soil air and groundwater after spill for 2-ethylhexyl nitrate
The compound is not identified with the analytical programs generally used for soil air and groundwater after fuel spills, but analysis with the required limit of detection is probably possible.
2-Ethylhexan-1-ol, CAS 104-76-7 The risk assignment for the additive compound 2-ethylhexan-1-ol, structural formula in Figure 11.5, is based upon declared lower and upper limits of the dosage used for diesel and gasoline, and in addition on an upper and lower limit declared for the concentration of this compound in the four products in question. An expected and realistic maximum groundwater concentration could not be estimated due to the very variable concentra-tions and dosages.
The compound is without human health risk classifications that would add risk in case of a fuel spill. With respect to the environmental risk classification, two safety data sheets declare that the compound is toxic to aquatic organisms and may cause long term adverse effects in the aquatic environment (R51/53), while one uses the classification R51 only, and one uses no environmental classification at all. The classification used here was N: R51/53 reflecting the most cautious interpretation of the manufacturer safety data sheets. The compound is a biocide as it is listed as such in Part A of Annex V of the EU Biocide Directive implementation document.
The compound is aerobically but not anaerobically readily biodegradable. It should be recalled that the compound may also be formed by abiotic hydrolysis of 2-ethylhexyl ni-trate, see above.
65
As the compound is not anaerobically degradable and mobile, it could be transported with groundwater ahead of fuel based contaminants, see Figure 11.1, upper right. The classification as very environmentally hazardous for aquatic organisms would lead to concern for fresh waters impacted by groundwater contaminated by this compound.
Figure 11.5 Structural formula for 2-ethylhexan-1-ol.
With a maximum content of 32% of 2-ethylhexan-1-ol in an additive product and a maximum dosage of the product of 900 ppm, the highest concentration of the compound in fuel products would be 290 mg/L. A 1000 L fuel spill would thus release 290 g 2-ethylhexan-1-ol and the highest volume contaminated to the maximum concentration of 1000 µg/L would be 1 m3, Table 11.10.
Matrix Threshold m
3 contamina-
ted to thres-
hold
Estimated ma-
ximum con-
centration ran-
ge
m3 contami-
nated to maxi-
mum concen-
tration
Groundwater 0.1 µg/L 2,900,000 2.7-250 µg/L 1,200
Table 11.10 Estimated effects on groundwater after spill for 2-ethylhexan-1-ol.
The compound is not identified with the analytical programs generally used for groundwater after fuel spills, but analysis with the required limit of detection is proba-bly possible.
11.2.2 Surface active additives The term “surface active additives” or “surfactant additives” is used to describe the group of additive compounds of with a polar group and a large apolar group. These compounds will have the properties of surface active compounds or detergents in com-mon, but may in reality be added for other purposes. Generally, many of these com-pounds are less well defined in structure, often with varying sidechain lengths, and both chemical-physical data and human health and environmental risk classifications may be limited. Frequently, the polar groups are ionisable making the interpretation of the physical-chemical data less straight forward as the data may refer to both unionized and ionized forms. Furthermore, several of the compounds in this group also contain polym-erized groups and may thus belong to the group of polymers as well.
The main groups of surface active additives used in Denmark were:
• Alkylsuccinimides
66
• Polyalkoxylates
• Alkylamines
• Alkylated organic acids
• Mannich bases.
The surface active additives are further discussed below.
Alkylsucinimides
Two additives belonging to this group have been reviewed for human health and envi-ronmental properties in a test plan submitted for the US EPA High Production Volume (HPV) Challenge Program /110/. A representative of the alkylsuccinimide structures is given in Figure 11.6. It should be noted that the US EPA has asked for additional in-formation with respect to the ecotoxicological properties of representatives of this group.
Figure 11.6 Structural formula for a representative from the alkylsuccinimide group of surface active addi-tives, from /111/.
With the data from the review used in the risk screening procedure for additives from this group used in Denmark, it is suggested that these additives will no contribute added risk to fuels in case of spills.
Alkoxylates
This group of surface active additives used in Denmark comprises a broad group of compounds with an apolar alkyl or alkyl aryl group and a polar (poly)alkoxylate group: alcohol alkoxylates, alkylphenol alkoxylates and fatty acid alkoxylates, see Figure 11.7 for the structural formula for a representative of the group.
Using the data available from the additive producers and open sources including model-ling for additives from this group used in Denmark, it is suggested that these additives will no contribute added risk to fuels in case of spills. It should be noted though that one additive compound from this group has not been identified by the producer.
67
Figure 11.7 Structural formula for representative of alkoxylates, a polypropyxylated dodecylphenol.
Alkylamines
This group of compounds used in Denmark in additive products includes a small num-ber of technical mixtures of polyalkenes with one or more amino groups. For three addi-tive compounds, the risk screening suggested an added risk after a spill from the com-pounds in fuels, whereas one additive compound was suggested to be without added risk.
1,2-ethanediamine reaction products with chlorinated polyisobutylene, CAS 68891-
84-9 The risk assignment for the additive compound 1,2-ethanediamine reaction products with chlorinated polyisobutylene, no structural formula available, is based upon de-clared dosage used for gasoline, and in addition upon declared concentration of this compound in the product in question. An expected and realistic maximum groundwater concentration would be 1,500 µg/L and maximum soil air concentration 27 mg/m3 esti-mated from the declared dosage.
It should be noted that 1,2-ethanediamine reaction products with chlorinated polyisobu-tylene is an ionizable “compound”, where the water solubility has been calculated from an estimated maximum water solubility for the unionized compounds as declared by the additive producer with correction for ionization, see section 11.1.9. The additive pro-ducer has commented that an experimental water solubility for the ionized compound to his knowledge is not available. The vapor pressure used has been declared by the pro-ducer.
The compound is without human health risk and environmental classifications that would add risk in case of a fuel spill. Still, it should be emphasized that not all the ecotoxicity data required for the classification have been made available.
The compound is neither aerobically, nor anaerobically readily biodegradable.
As the compound is mobile and not degradable, it could be transported with groundwa-ter ahead of fuel based contaminants, see Figure 11.1, upper right. As the compound is
HO
H3C
O
H3C
O CH3
O
CH3
O
CH3
OH3C
O
H3C
O
H3CO CH3
O
CH3
O
CH3
OH3C
OH3C
H3C
H3C
H3CCH3
68
considered volatile with the data available and in spite of the high declared molecular weight, it could impact the soil and indoor air.
With a content of 15% of 1,2-ethanediamine reaction products with chlorinated poly-isobutylene in an additive product and a dosage of the product of 1020 ppm, the maxi-mum concentration of the compound in fuel products would be 150 mg/L. A 1000 L fuel spill would thus release 150 g 1,2-ethanediamine reaction products with chlorinated polyisobutylene. The highest volume of groundwater contaminated to the maximum concentration of 1,500 µg/L would be 100 m3 and of soil air to the maximum concentra-tion of 27mg/m3 would be 5,600 m3, see Table 11.11.
Matrix Threshold m
3 contamina-
ted to thres-
hold
Estimated ma-
ximum con-
centration
m3 contami-
nated to maxi-
mum concen-
tration
Groundwater 10 µg/L 1,500 1,500 µg/L 100
Soil air 0.5 mg/m3 300,000 27 mg/m
3 5,600
Table 11.11 Estimated effects on groundwater and soil air after spill for 1,2-ethanediamine reaction pro-ducts with chlorinated polyisobutylene
The compound is not identified with the analytical programs generally used for soil air and groundwater after fuel spills, and analysis with the required limit of detection will probably not be readily available.
1-Propene, 2-methyl-, homopolymer, hydrofomylation products, reaction products
with ammonia, CAS 337367-30-3 The risk assignment for the additive compound 1-propene, 2-methyl-, homopolymer, hydrofomylation products, reaction products with ammonia (termed polyisobutylene amine), no structural formula available, is based upon declared dosages used for gaso-line, and in addition upon declared concentrations of this compound in the three prod-ucts in question. An expected and realistic maximum groundwater concentration would be 100 µg/L.
It should be noted that the polyisobutylene amine is an ionizable compound, and that the maximum water solubility declared by the additive producer has been used in the risk screening.
The compound is without human health risk and environmental classifications that would add risk in case of a fuel spill, see the discussion in section 11.1.10. Still, it should be emphasized that the classifications are as declared by the producer without documentation.
The compound is neither aerobically, nor anaerobically readily biodegradable.
As the compound is mobile and not degradable, it could be transported with groundwa-ter ahead of fuel based contaminants, see Figure 11.1, upper right.
With a content of 30% of polyisobutylene amine in an additive product and a dosage of the product of 1200 ppm, the maximum concentration of the compound in fuel products
69
would be 360 mg/L. A 1000 L fuel spill would thus release 360 g polyisobutylene amine. The highest volume of groundwater contaminated to the maximum concentration of 180 µg/L would be 2,000 m3, see Table 11.12.
Matrix Threshold m
3 contamina-
ted to thres-
hold
Estimated ma-
ximum con-
centration
m3 contami-
nated to maxi-
mum concen-
tration
Groundwater 10 µg/L 36,000 180 µg/L 2,000
Table 11.12 Estimated effects on groundwater and soil air after spill for polyisobutylene amine.
The compound is not identified with the analytical programs generally used for groundwater after fuel spills, and analysis with the required limit of detection will probably not be readily available.
Polyalkylene polyamine The risk assignment for the additive compound polyalkylene polyamine, no identity de-clared, no structural formula available, is based upon declared dosage used for gasoline, and in addition upon declared concentration of this compound in the product in ques-tion. An expected and realistic maximum groundwater concentration would be 550 µg/L estimated from the declared dosage. It should be noted that is an ionizable compound. In this risk screening, the water solu-bility has been declared by the producer (water miscible).
The compound is without human health risk classifications that would add risk in case of a fuel spill. The environmental risk classification given is “toxic to aquatic organ-isms” and “may cause long term adverse effects in the aquatic environment” (N: R51/53).
The compound is neither aerobically, nor anaerobically readily biodegradable.
As the compound is mobile and not degradable, it could be transported with groundwa-ter ahead of fuel based contaminants, see Figure 11.1, upper right.
With a content of 0.1% of polyalkylene polyamine in an additive product and a dosage of the product of 550 ppm, the maximum concentration of the compound in fuel prod-ucts would be 0.55 mg/L. A 1000 L fuel spill would thus release 550 mg polyalkylene polyamine. The highest volume of groundwater contaminated to the maximum concen-tration of 550 µg/L would be 1 m3, see Table 11.13.
The compound is not identified with the analytical programs generally used for groundwater after fuel spills, and analysis with the required limit of detection will probably not be readily available.
70
Matrix Threshold m3 contamina-
ted to thres-
hold
Estimated ma-
ximum con-
centration
m3 contami-
nated to maxi-
mum concen-
tration
Groundwater 0.1 µg/L 5,500 550 µg/L 1
Table 11.13 Estimated effects on groundwater and soil air after spill for polyalkylene polyamine.
It should be noted that this compound is not in itself considered an additive but is a re-sidual monomer that may occur in some surface active additives to varying but gener-ally low concentrations.
Alkylated organic acids
This group of compounds used in Denmark in additive products includes a small num-ber of compounds based upon butane- or butenedioic acid. For three additive com-pounds, the risk screening suggested an added risk after a spill from the compounds added to fuels, whereas one additive compound was suggested to be without added risk. Additionally, the group comprised an organic sulphonic acid where the risk screening suggested an added risk for groundwater.
Maleic acid tridecylamide, CAS 84583-68-6 The risk assignment for the additive compound maleic acid tridecylamide, no structural formula available, is based upon declared lower and upper limits of the dosage used for gasoline, and in addition on an upper and lower limit declared for the concentration of this compound in the two products in question. An expected and realistic maximum groundwater concentration would be 260 µg/L estimated from declared typical dosages.
It should be noted that maleic acid tridecylamide is an ionizable compound, where the water solulibility has been estimated for the risk screening using EPIwin 3.11 with cor-rection for ionization, see section 11.1.9. The additive producer has commented that the estimated water solubility is too high but has not provided documentation allowing for setting a lower value.
The compound is without human health risk and environmental classifications that would add risk in case of a fuel spill.
The compound is neither aerobically, nor anaerobically readily biodegradable.
As the compound is mobile and not degradable, it could be transported with groundwa-ter ahead of fuel based contaminants, see Figure 11.1, upper right.
With a maximum content of 3% of maleic acid tridecylamide in an additive product and a maximum dosage of the product of 1,200 ppm, the highest concentration of the com-pound in fuel products would be 36 mg/L. A 1000 L fuel spill would thus release 36 g maleic acid tridecylamide, and the highest volume contaminated to the maximum con-centration of 1,400 µg/L would be 26 m3, Table 11.14.
The compound is not identified with the analytical programs generally used for groundwater after fuel spills, but analysis with the required limit of detection may be possible.
71
Matrix Threshold m
3 contamina-
ted to thres-
hold
Estimated ma-
ximum con-
centration
m3 contami-
nated to maxi-
mum concen-
tration
Groundwater 10 µg/L 3,600 1,400 µg/L 26
Table 11.14 Estimated effects on groundwater after spill for maleic acid tridecylamide.
Tetrapropenylbutanedioic acid, CAS 27859-58-1 The risk assignment for the additive compound tetrapropenylbutanedioic acid, structural formula in Figure 11.8, is based upon declared dosage used for gasoline, and in addition upon declared concentration of this compound in the product in question. An expected and realistic maximum groundwater concentration would be 32 µg/L estimated from declared typical dosage. It should be noted that tetrapropenylbutanedioic acid is an ionizable compound, where the water solubility has been estimated for the risk screening using EPIwin 3.11 with correction for ionization, see section 11.1.9. The additive producer has commented that the estimated water solubility is too high but has not provided documentation allowing for setting a lower value.
The compound is without human health risk and environmental classifications that would add risk in case of a fuel spill. Still, it should be emphasized that not all the ecotoxicity data required for the classification have been made available and a classifi-cation as very environmentally hazardous (N: R51/53) may be more correct than the classification used (R52/53) used to provide the 10 µg/L groundwater threshold.
The compound is not aerobically readily biodegradable, and no data are available for anaerobic degradability.
As the compound is mobile and not degradable, it could be transported with groundwa-ter ahead of fuel based contaminants, see Figure 11.1, upper right.
Figure 11.8 Structural formula for tetrapropenylbutanedioic acid.
With a content of 1.1% of tetrapropenylbutanedioic acid in the additive product and a dosage of the product of 130 ppm, the concentration of the compound in fuel products would be 1.4 mg/L. A 1000 L fuel spill would thus release 1.4 g tetrapropenylbuta-nedioic acid, and the highest volume contaminated to the maximum concentration of 32 µg/L would be 44 m3, Table 11.15.
72
Matrix Threshold m3 contamina-
ted to thres-
hold
Estimated ma-
ximum con-
centration
m3 contami-
nated to maxi-
mum concen-
tration
Groundwater 10 µg/L 140 32 µg/L 44
Table 11.15 Estimated effects on groundwater after spill for tetrapropenylbutanedioic acid.
The compound is not identified with the analytical programs generally used for groundwater after fuel spills, but analysis with the required limit of detection may be possible.
1,2-bis(2-ethylhexyloxycarbonyl)ethanesulphonate potassium salt, CAS 7491-09-0 The risk assignment for the additive compound 1,2-bis(2-ethylhexyl-oxycarbonyl)ethanesulphonate potassium salt, structural formula in Figure 11.9, is based upon declared lower and upper limits of the dosage used for gasoline, and in addi-tion on an upper and lower limit declared for the concentration of this compound in the three products in question. An expected and realistic maximum groundwater concentra-tion would be 2,200 µg/L estimated from declared typical dosages.
The additive producer has commented that the additive will, based upon available data, not result in adverse effects after release to the environment, and that this assessment has been accepted by the US EPA.
The compound is without human health risk and environmental classifications that would add risk in case of a fuel spill. Still, it should be emphasized that not all the ecotoxicity data required for the classification have been made available.
The compound is aerobically readily biodegradable, but no data are available for an-aerobic degradability.
As the compound is mobile and not degradable, it could be transported with groundwa-ter ahead of fuel based contaminants, see Figure 11.1, upper right.
With a content of 12.5% of 1,2-bis(2-ethylhexyloxycarbonyl)ethanesulphonate potas-sium salt in an additive product and a dosage of the product of 800 ppm, the maximum concentration of the compound in fuel products would be 100 mg/L. A 1000 L fuel spill would thus release 100 g 1,2-bis(2-ethylhexyloxycarbonyl)ethanesulphonate potassium salt, and the highest volume contaminated to the maximum concentration of 32 µg/L would be 44 m3, Table 11.16.
73
Figure 11.9 Structural formula for 1,2-bis(2-ethylhexyloxycarbonyl)ethanesulphonate potassium salt.
Matrix Threshold m3 contamina-
ted to thres-
hold
Estimated ma-
ximum con-
centration
m3 contami-
nated to maxi-
mum concen-
tration
Groundwater 10 µg/L 10,000 2,400 µg/L 42
Table 11.16 Estimated effects on groundwater after spill for 1,2-bis(2-ethylhexyloxycarbonyl)ethanesulphonate potassium salt
The compound is not identified with the analytical programs generally used for groundwater after fuel spills, and analysis with the required limit of detection may not be readily available.
Manich bases
This group of compounds used in Denmark in additive products includes a small num-ber of compounds with alkylphenol groups linked by amines. For one of two additive compounds, the risk screening suggested an added risk after a spill from the compounds added to fuels.
Polyolefin Mannich base The risk assignment for the additive compound polyolefin Mannic base, an alkylphe-nolamine, no structural formula available, is based upon declared upper limit of the dos-age used for gasoline, and in addition on the declared concentration of this compound in the products in question. An expected and realistic maximum groundwater concentra-tion would be 800 µg/L estimated from declared typical dosage.
It should be noted that the polyolefin Mannic base is an ionizable compound, where the water solubility has been estimated for the risk screening using EPIwin 3.11 with cor-rection for ionization, see section 11.1.9. The additive producer has commented that the estimated water solubility is too high but has not provided documentation allowing for setting a lower value.
H3C
CH3
O
O
S
O
O
OH
O
O
H3C
74
The compound is without human health risk and environmental classifications that would add risk in case of a fuel spill. Still, it should be emphasized that the classifica-tions are as declared by the producer without documentation.
The compound is neither aerobically, nor anaerobically readily biodegradable.
As the compound is mobile and not degradable, it could be transported with groundwa-ter ahead of fuel based contaminants, see Figure 11.1, upper right.
With a content of 2.6% of the polyolefin Mannic base in an additive product and a dos-age of the product of 800 ppm, the maximum concentration of the compound in fuel products would be 21 mg/L. A 1000 L fuel spill would thus release 21 g the polyolefin Mannic base, and the highest volume contaminated to the maximum concentration of 840 µg/L would be 44 m3, Table 11.17.
Matrix Threshold m
3 contamina-
ted to thres-
hold
Estimated ma-
ximum con-
centration
m3 contami-
nated to maxi-
mum concen-
tration
Groundwater 10 µg/L 2,100 840 µg/L 26,000
Table 11.17 Estimated effects on groundwater after spill for the polyolefin Mannic base.
The compound is not identified with the analytical programmes generally used for groundwater after fuel spills, and analysis with the required limit of detection may not be readily available.
It should be noted that the producer declaring use of this additive compound has stated that the additive product in question it is no longer used in the EU (2006).
11.2.3 Polymers The term “polymers” is used here for simple polymer additives such a polyacetates, polyamides and polyalkenes. It should be noted that several of the surface active addi-tives, see section 11.2.2, are also polymers.
At the least 6 different simple polymers were declared in additive products used in Denmark, most with limited information on identities and structures. These compounds are without declared human health risk and environmental classifications that would add risk in case of a fuel spill, and the risk screening did not suggest an added risk from them.
Furthermore, siloxanes have been declared in three additive products used for diesel in Denmark. No added risk was suggested in the risk screening, but for two of the siloxane additives, the information was incomplete with missing identity, vapor pressure and/or classifications.
11.2.4 Monomers The term “monomers” is here used for lowmolecular weight compounds that are po-lymerized to produce polymer additives. It should be noted that a clear distinction can
75
not always be made between monomers and reagents for synthesis of complicated or-ganic compounds.
The main monomer types used in production of polymer additives used in Denmark are summarized in Table 11.18. Several of the monomers are of considerable human health and environmental concern, mobile, volatile and/or persistent in the aqueous environ-ment.
Types Reactive
gasses
Amines Alkyl-
phenols
Alkenyl
esters
Organic
acids
Formalde-hyde
Alkylamines Dodecyl-phenols
Acetic acid ethenyl ester
Butanedioic acid
Alkylene-oxides
Polyalkylpo-lyamines
Examples
Alkenes
Table 11.18 Main monomer types used in production of polymeradditives used in Denmark.
The concentrations of the compounds were generally declared as <0,5 ppm to <0,1%, but also as “negligible” or “no residual monomer”. It was not always clear whether such maximum concentrations pertained to the polymer additive or to the additive product. In Table 11.19, the risk screening is done for two known monomers with examples of maximum monomer concentrations and assumed 10% polymer additive in the additive product and assumed additive product dosage of 0.1 % to the fuel product.
Monomer
concen-
tration
Threshold Maximum con-
centration in
soil water
Maximum con-
centration in
soil air
Soil water Soil air
<0.01% 10 µg/L 3x10-4 mg/m3 Ethylene-
diamine <1 ppm
10 µg/L 0,5 mg/m3
0.1 µg/L 3x10-6 mg/m3
<0.1% 10 µg/L 3x10-2 mg/m3
<1 ppm 0.1 µg/L 3x10-4 mg/m3
Ethylene oxide
<0.01 ppm
0.1 µg/L 1x10-6
mg/m3
0.001 µg/L 3x10-6 mg/m3
Table 11.19 Illustrative risk screening for two monomer examples from assumed additive products and
dosages.
The worked examples show that polar, water soluble monomers such as ethylenedia-mine should be below 0.01% in the polymer used to produce the additive product in or-der to ensure not exceeding soil water thresholds for additive compounds without classi-fications as toxic, very toxic and/or very environmentally hazardous. For monomers with such classifications, the concentrations should be below 1 ppm. Similarly, volatile and toxic monomers such as ethylene oxide should be below 0.01 ppm in the polymer in order to ensure not exceeding soil air thresholds, whereas the monomer concentrations of monomers without classification as toxic or very toxic should be below 1% in the polymer. It should be noted that these considerations do not consider any added soil risk.
76
The currently available data on monomers do not allow for a risk screening as outlined here, mainly because quantitative information on monomer identities and concentrations in the required range are not available.
11.2.5 Proprietary ingredients Not all additive compound identities were disclosed and data were not given for some additives. The missing information is summarized in chapter 10 and should be consid-ered in the evaluation of the results from the risk screening.
77
78
12 CONSOLIDATION
In order to qualify the identification of potential risk additives in Danish gasoline and diesel, the information obtained from open sources and from the additive producers was consolidated. Furthermore, the risk screenings were put into perspective by comparison with additives of known and acknowledged risk.
12.1 Structural groups of additives with risk for human health or the environment
For the structural groups found to indicate a risk for human health and/or the environ-ment, see section 8.1 for explanation and Table 8.2 for structural groups, additive com-pounds were identified as used in Denmark for 4 groups, and for 2 groups with 4 repre-sentative with particular risk for the environment, see Table 12.1. It should be noted that among the 7 phenols used as additives or found as additive contaminants, 3 were very environmentally hazardous with classifications N: R50/53 or N: R51/53.
Overall, no additives with classifications as toxic or very toxic were identified as used in Denmark. Totally, 10 additives with classifications as very environmentally hazard-ous were identified as used in Denmark. It should be remembered here, that a large group of additive compounds were not identified and that classification data were in-complete for a large group of compounds as well.
Particular human health risk Very environmentally hazardous
Represen-tatives used in Denmark
Actual, par-ticular risk classifications
Representa-tives used in Denmark
Actual, par-ticular risk classifications
Alkyl leads None None Alkyl leads None None
Metal carbonyls
None None Metal carbonyls
None None
Amines 4 com-pounds
None Amines 4 compounds 1 with N: R51/53
Alkyl nitrates 1 com-pound
None Quaternary ammonium compounds
1 compound None
Alcohols and phenols
7 com-pounds
3 compounds Short chain halogenated alkanes
None None
Short chain halogenated alkanes
None None Heterocyclic compounds
None None
Phthalates None None Peroxides None None
Table 12.1 Structural groups of additives with particular risk for human health and/or the environment with indication of declared use in Denmark and actual classifications.
79
12.2 Structural groups of additives with risk for distribution into mobile phases
For the structural groups found to indicate a risk of distribution into mobile phases, see Table 8.4, additive compounds were identified as used in Denmark for 6 groups, and for the 4 groups with risk for distribution into groundwater, added groundwater risk was in-deed suggested in the risk screening, see Table 12.2.
Risk for groundwater with > 10% distribu-
tion into water
Risk for air or indoor air with > 10% distri-
bution into air
Representa-tives used in Denmark
Added risk suggested
Representa-tives used in Denmark
Added risk suggested
Organic ac-ids and their salts
8 compounds Added risk for ground-water for 3 compounds
Short chain ethers
1 compound None
Short chain alcohols and glycols
2 compounds Added risk for ground-water for 2 compounds
Short chain alkenes
None None
Alcohol amines
2 compounds Added risk for ground-water for 2 compounds
Siloxanes 3 compounds None, insuffi-cient informa-tion for 2
Short chain aldehydes and ketones
None None
Short chain ethers
1 compound Known risk for ground-water for 1 compound
Heterocyclic compounds
No simple heterocyclic compounds
None
Alkyl carbon-ates
None None
Urea None None
Table 12.2 Structural groups of additives with particular risk for distribution into mobile phases with indica-tion of declared use in Denmark and suggested added risk.
12.3 Danish additive consumption from open sources
For the 13 additives used in Denmark above 2 t in 2001 according to the SPIN database, see Table 7.2, the risk screening results based upon additive producer data are shown in Table 12.3, see section 11.2 for the origin of the estimated concentrations.
80
CAS no. Compound name Used 2001
(t)
Declared
in additive
products
Risk screening re-
sult in additive pro-
ducts
Generic risk scree-
ning result
67 63 0 2-Propanol 29 Yes Up to 1000 µg/L in groundwater
-
102 71 6 Triethanolamine 99 No - Up to 105 µg/L in
groundwater
104 76 7 2-Ethyl-1-hexanol 912 Yes Up to 250 µg/L in groundwater
-
111 42 2 Diethanolamine 6.1 No - Up to 105 µg/L in
groundwater
111 76 2 2-Butoxy ethanol 29 No - Up to 105 µg/L in
groundwater
128 39 2 2,6-bis(1,1-Dimethylethyl)phenol 133 Yes No added risk sugge-sted
-
9003 29 6 Butene, homopolymer 3 (Yes)31
No added risk sugge-sted
-
25068 38 6 Epon 1001 Resin (4,4’-(1-Methylethylidene)-bis-phenol polymer with chlormethyloxiran, Bisphenol A epichlorhydrin copolymer))
9.6 No - Required data not available from open sources
27247 96 7 2-Ethylhexyl nitrate 1501 Yes Up to 26 µg/L in groundwater Up to 3.9 mg/m3 in soil air
-
61790 12 3 Tall oil fatty acids 3237 (Yes) No added risk sugge-sted
-
68123 18 2 Bisphenol-A reacted with ethyleneoxide, propyleneoxide or chlo-ropropyleneoxide
53 No - Required data not available from open sources
84583 68 6 (Z)-4-Oxo-4-(tridecylamino)-2-butenoic acid (Maleic acid tride-cylamide)
268 Yes Up to 250 µg/L in groundwater
-
84605 20 9 Polyethylenpolyamines reacted with polyisobutenyl succinic anhy-dride
508 Yes No added risk sugge-sted
-
Table 12.3 Additives identified as used in Denmark 2001 above 2 t compared to additives declared in additive products.
31 Similar compounds have been declared and subjected to the risk screening. 81
82
For additives used in Denmark according to the SPIN database but not declared as com-ponents of additive products exported to Denmark by petroleum companies/additive producers, a “generic risk screening” was done using the procedure described in section 11, assuming 10% active additive compound in the additive product and 1,000 ppm (1‰) dosage of the additive product in the fuel product. The product composition and product dosage assumption can be considered realistic, but in the upper range for this type of additives and therefore as precautionary. For the two polymeric compounds (the Epon 1001 Resin and the bisphenol-A polymer), the data required for the risk screening could not be found in open sources. It should be noted that Epon 1001 Resin is classi-fied as very environmentally hazardous, N: R51/53.
The results of the generic risk screenings are summarized in Table 12.4 using the same format as for the additives with suggested added risk as based upon data from the addi-tive producers, see section 11.2.
Additive com-
pound
Threshold m3 contamina-
ted to thres-
hold
Estimated ma-
ximum con-
centration
m3 contami-
nated to maxi-
mum concen-
tration
Diethanolamine 10 µg/L 10,000 105 µg/L 1
Triethanolamine 10 µg/L 10,000 105 µg/L 1
2-Buthoxy etha-nol
10 µg/L 10,000 105 µg/L 1
Table 12.4 Estimated effects on groundwater after spill for the 3 fuel additives imported above 2 t in 2001
according to the SPIN database.
It should be noted that these compounds are readily biodegradable under aerobic condi-tions, but without sufficient data for anaerobic biodegradation.
As the compounds are not proven anaerobically degradable and mobile, they could be transported with groundwater ahead of fuel based contaminants, see Figure 11.1, upper right.
12.4 Risk comparison
The risk screening did not identify any additive compounds known to be used in Den-mark with added risk at direct soil exposure, see section 11 for explanation.
For two compounds, an added risk for soil air was suggested in the risk screening: 2- ethylhexyl nitrate (2-EHN) and 1,2-ethanediamine reaction products with chlorinated polyisobutylene (EDP). The relative risk is illustrated in Figure 12.1 with tetraethyl lead (TEL) and 1,2-dichloroethane (DCA) given for comparison. The volume of soil air log of volume in m3 contaminated to the maximum concentration in soil air (log of concen-tration in mg/m3) is plotted against the maximum concentration, assuming a spill of 1000 L of fuel and using the assessments presented previously, see sections 11 and 11.2. The “degree of concern” associated with the additive is shown with the size of the “bubbles” where compounds without classifications of particular concern with respect to human health (T or Tx) and environmental hazard (N) have a small bubble (radius 1),
83
with classification N a larger (radius 2), with classification T or Tx still larger (radius 3) and both T/Tx and N the largest bubble (radius 4), see section 11 for explanation.
Note: 2-EHN is 2-ethylhexyl nitrate, TEL is tetraethyl lead, DCA is 1,2-dichloroethane, EDP is 1,2-ethanediamine reaction products with chlorinated polyisobutylene.
Figure 12.1 Illustration of the soil air risk associated with acknowledged risk additives and additives with risks suggested in the risk screening, see text for explanation.
In summary, tetraethyl lead would contaminate a large volume of soil air to a compara-tively low concentration, but is of considerable concern for both human health and the environment. 2-Ethylhexyl nitrate has the same pattern of concentration and volume, but is of much less concern. 1,2-Dichloroethane would contaminate a small volume to a high concentration and is of concern for human health. For 1,2-ethanediamine reaction products with chlorinated polyisobutylene, the contaminant concentration, the contami-nated volume and the concern are less than for the other three compounds.
Said in other words: large bubbles in the upper right corner of Figure 12.1 must be taken very seriously, whereas small bubbles in the lower left corner are of less concern.
Similarly, the 13 additive compounds with suggested risk for groundwater are plotted in Figure 12.2 with 1,2-dichloroethane and methyl-tert-butyl ether (MTBE) plotted for comparison.
The overall picture is that none of the additives identified as used in Denmark and with a suggested risk for groundwater would contaminate groundwater to the same high con-
0
1
2
3
4
5
6
7
0 1 2 3
Log concentration
Lo
g v
olu
me
DCA
TEL
2-EHN
EDP
0
1
2
3
4
5
6
7
0 1 2 3
Log concentration
Lo
g v
olu
me
DCA
TEL
2-EHN
EDP
84
centrations as MTBE, but compounds such as diethanolamine (DEA), triethanolamine (TEA) and 2-buthoxy ethanol (2-BE) have a potential for contaminating large volumes of groundwater to high concentrations.
Conversely, 2-ethylhexane-1-ol (2-EHA) and to some degree 2-ethylhexyl nitrate (2-EHN) would contaminate large volumes of groundwater to lower concentrations.
Note: 2-EHA is 2-ethylhexane-1-ol, 2-EHN is 2-ethylhexyl nitrate, PHF is 1-propene, 2-methyl-, ho-mopolymer, hydrofomylation products, reaction products with ammonia, PAPA is polyalkylene poly-amine, SUK is 1,2-bis(2-ethylhexyloxycarbonyl)ethanesulphonate potassium salt, MAN is polyoelfin Mannich bases, MAL is maleic acid tridecylamide, DEA is diethanolamine, TEA is triethanolamine, 2-BE is 2-buthoxy ethanol, EDP is 1,2-ethanediamine reaction products with chlorinated polyisobutylene, IPA is 2-propanol, DCA is 1,2-dichloroethane, TPA is tetrapropenylbutanedioic acid, MTBE is methyl-tert-butyl ether.
Figure 12.2 Illustration of the groundwater risk associated with acknowledged risk additives and additives with risks suggested in the risk screening, see text for explanation.
12.5 Risk summary
Considering the results of the risk screening, the quality of the data used in the screen-ing and the human health and environmental concern, the risk assignments are summa-rized in Table 12.5 for those additive compounds known to be used in Denmark where an added risk can not be excluded.
Additive compounds known to be used in Denmark where an added risk may not be ex-cluded due to lack of data have been summarized in Table 12.6. For these compounds, additional data should be made available with respect to water solubility considering the ionizable nature of the compounds and for one compound, the vapor pressure should be verified, if necessary experimentally.
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
Log concentration
Lo
g v
olu
me
2-EHA
DEA
TEA2-BESUK
EDP
PAPA
PHF
MANMAL
IPA DCA
2-EHN
TPA
MTBE
0
1
2
3
4
5
6
7
8
0 1 2 3 4 5 6 7 8
Log concentration
Lo
g v
olu
me
2-EHA
DEA
TEA2-BESUK
EDP
PAPA
PHF
MANMAL
IPA DCA
2-EHN
TPA
MTBE
85
In evaluating the structural types of additive compounds that may cause an added risk for groundwater, the following should be mentioned:
• Short chain alcohols and ethers
• Alkylamines
• Organic acids
• Other ionized or ionizable organic compounds.
In particular, it must be underlined that the use of highly water soluble or volatile addi-tives will imply a risk of contaminating groundwater or air, respectively, to high con-centrations, in particular if they are also persistent in the soil groundwater environment. One example of very water soluble, persistent additive compounds that will occur in fuel contaminated groundwater if used as additives are the dialkyl ether analogs to MTBE such as e.g.: methyl-tert-amyl ether (TAME), ethyl-tert-butyl ether (ETBE), di-iso-propylether (DIPE).
The risk that may be associated with monomers used for production of polymers used as fuel additives should be evaluated, preferentially by controlling the monomer contents at sufficiently low concentrations. Some of the monomers are reactive and of consider-able concern for human health and/or the environment.
In evaluating the risk summary, it should be recalled that a number of additive com-pounds have not been identified, are without sufficient data and/or are without accepted, documented and complete classifications, see chapter 10 for details on the number of incomplete declarations on additive compounds for the different additive producers. In particular for a range of polymer and/or surface active additives, the data on structure, properties and effects was found insufficient for the risk screening.
Finally, it should be emphasized that the risk screening is not a full risk assessment. For the additive compounds where an added risk could not be excluded in the risk screen-ing, it is consequently suggested to launch a full risk assessment including scenario based assessments of the risks for soil air and groundwater associated with fuel spills in Denmark. Furthermore, it is suggested to investigate the historical and present use of these compounds and to include those used over longer periods or still used in the moni-toring programs at fuel spill sites.
86
CAS no. Compound name Abbreviation Added risk for
groundwater
Added risk for
soil air
67 63 0 2-Propanol IPA Yes No
102 71 6 Triethanolamine TEA Yes No
104 76 7 2-Ethyl-1-hexanol 2-EHA Yes No
111 42 2 Diethanolamine DEA Yes No
111 76 2 2-Butoxy ethanol 2-BE Yes No
7491 09 0 1,2-bis(2-Ethylhexyloxycarbonyl)ethanesulphonate potassium salt SUK Yes No
27247 96 7 2-Ethylhexyl nitrate 2-EHN Yes Yes
Polyalkylene polyamine PAPA Yes No
Table 12.5 Additive compounds used in Denmark where an added risk could not be excluded in the risk screening.
CAS no. Compound name Abbreviation Added risk for
groundwater
Added risk for
soil air
27859 58 1 Tetrapropylenebutanedioic acid TPA (Yes)32
No
337367 30 3 1-Propene, 2-methyl-, homopolymer, hydroformylation products, reaction products with ammonia
PHF (Yes) No
68891 84 9 1,2-Ethanediamine reaction products with chlorinated isobutylene EDP (Yes) (Yes)
84583 68 6 (Z)-4-Oxo-4-(tridecylamino)-2-butenoic acid (Maleic acid tride-cylamide)
MAL (Yes) No
Polyolefin Mannich base MAN (Yes) No
Table 12.6 Additive compounds used in Denmark where an added risk could not be excluded in the risk screening, potentially due to lack of data.
32 (): the risk assignment is preliminary only and additional data are required 87
88
13 CONCLUSIONS AND RECOMMENDATIONS
A range of additives are added to fuels such as gasoline and diesel and in case of spill, some of these may imply an added risk (see below for explanation) to soil, air and groundwater as com-pared to the spill of petroleum derived fuel components only. Additives such as MTBE, tetra-ethyl lead and 1,2-dichloroethane are acknowledged examples of the potential impact of fuel ad-ditives in case of spill.
Therefore, an inventory has been performed based upon both open and confidential sources of information in order to exclude from consideration all such gasoline and diesel additive com-pounds that do not imply an added risk in case of a fuel spill. Part of the inventory has been to evaluate the accessibility of information on fuel additives. In the context of this inventory, addi-tives include oxygenates (blending products excluding petroleum fractions), functional additives and performance additives.
With respect to compounds and products, such as additives, Danish and EU regulations require that:
• Classification of all additives present above 0.1% in additive products or in petroleum prod-ucts handled in Denmark is available for the importer
• Notification of all additives classified as dangerous is done from the importer to the DEPA
• Registration of all additives classified as dangerous and with yearly import/production above 100 kg is done to the AT and registration in the Product Register.
The screening for risk additives show that for some additives, classifications where not sup-ported by data for all end points (i.e.: classification data are not always complete). The informa-tion on those additives classified as dangerous is furthermore not complete in the Danish regis-ters. Official and acknowledged classifications are available only for very few additives.
Additive identities and concentrations in additive products as well as additive product dosages to petroleum products are considered highly proprietary by additive producers and petroleum com-panies and accordingly, limited information on this is publically available. Overall, data retrieved from open sources can be considered to give only part of the picture of Danish fuel additive con-sumption and risks.
The Danish fuel market is dominated by a limited number of fuel suppliers depending mostly upon only two Danish refineries. Insight into the use of additives needs thus not be complicated. Based upon the available data on fuel and additive consumption in Denmark, the total Danish market for gasoline and diesel additives is estimated to between 15 and 90 million DKR, thus justifying a requirement for documentation of the environmental and human health safety of ad-ditives used.
Treat levels of additive compounds will depend upon the product, the fuel distributor, the refin-ery and the additive producer but the main feature is that typical additive concentrations are:
89
• Oxygenates 1 - 10 %
• Anti-icing additives 0.1 - 1 %
• Cetane improvers 0.1 %
• Other additives 1 ppm – 0.1 %.
In general, the additives used in gasoline and diesel are selected in response to a combination of technical, regulatory, environmental and economical incentives. Also, a large number of new patents on fuel additives are taken every year. The main focus for new additives is now upon polymer and surface active additives. For these additive groups, property data are less readily available than for the “classic”, simple additive compounds.
Previous experience with lead and manganese additives shows that using an element such as lead or manganese of potential human health and/or environmental concern as fuel additive should be considered carefully. Emission with exhaust can not be avoided and the potential impact upon air and soil quality will be challenged.
Previous and present use of oxygenates show that use of compounds with high water solubility and slow biodegradation as additives will imply risk of high concentration groundwater con-tamination.
The lesson from a small number of studies on the distribution properties of other fuel compo-nents is that polar, water soluble fuel components such as phenols and aromatic amines may end up in groundwater to high concentrations (mg/L), but that detection of the compounds is not to be expected in routine investigations.
Evaluation of the open source information on additives used internationally and in Denmark showed that some of the potential fuel additives could constitute a risk for groundwater as polar, water soluble compounds, whereas the number of compounds that could constitute a risk for air and indoor air was limited. Strucural groups that imply need for carefull evaluation if present in additives were identified.
To supplement the open source information on additives used in Denmark, further information was retrieved from the 5 Danish petroleum companies and the 5 major suppliers of additives to the Danish market. In all, 95 additive compounds in 34 additive products were screened for added risk in case of fuel spill. Some additive compounds were not identified (21) and/or not as-sociated with the property data and classifications needed in the screening (9).
The screening for potential risk additives was done as a filtering process removing those com-pounds that with high probability will be of no added risk (compared to the inherent gasoline or diesel constituents) after a spill. The end points considered were soil, air and groundwater, and thresholds were based upon Danish maximum contaminant concentrations. It should be noted that the screening process was not a full risk assessment and thus associated with the added un-certainty and precaution required in a simple screening approach with limited data available. Also, the screening process was not an identification of all potential risk compounds in fuel addi-tives, but as stated above only of those compounds that may impose an added risk as compared to inherent petroleum product constituents. Therefore, some additives not identified as at risk in
90
the current context as gasoline and diesel additives may be considered risk additives in another context, where the risks always associated with handling and using petroleum products are not present. In conclusion, the risk screening should be considered a removal from future investiga-tion programs for fuel spills of those compounds that are probably not risk compounds.
The screening showed that additive compounds classified as toxic or very toxic were not de-clared used as additives in Denmark. Totally 10 additives classified as very environmentally hazardous were declared as components in additive products used in Denmark.
No additives with an added risk for soil were identified. A list of 8 additive compounds of poten-tial risk to groundwater in case of fuel spill was established, see Table 13.1, and for one additive compound, a risk for air was suggested as well. It should be noted that only two of these addi-tives were classified as very environmentally hazardous. Also, the concentrations to be expected are probably lower than for e.g.: MTBE, but the affected volume of groundwater may be consid-erably larger. For the additive compounds suggested to be associated with an added risk in the risk screening, it is consequently suggested to launch a full risk assessment including scenario based assessments of the risks for soil air and groundwater associated with fuel spills in Den-mark. Furthermore, it is suggested to investigate the historical and present use of these com-pounds and to include those used over longer periods or still used in the monitoring programs at fuel spill sites.
CAS no. Compound name Added risk for
groundwater
Added risk for
soil air
67 63 0 2-Propanol Yes No
102 71 6 Triethanolamine Yes No
104 76 7 2-Ethyl-1-hexanol Yes No
111 42 2 Diethanolamine Yes No
111 76 2 2-Butoxy ethanol Yes No
7491 09 0 1,2-bis(2-Ethylhexyloxycar-bonyl)ethanesulphonate po-tassium salt
Yes No
27247 96 7 2-Ethylhexyl nitrate Yes Yes
Polyalkylene polyamine Yes No
Table 13.1 Additive compounds used in Denmark where an added risk could not be excluded in the risk screening.
91
CAS no. Compound name Added risk for
groundwater
Added risk for
soil air
27859 58 1 Tetrapropylenebutanedioic acid
(Yes)33
No
337367 30 3 1-Propene, 2-methyl-, ho-mopolymer, hydroformylation products, reaction products with ammonia
(Yes) No
68891 84 9 1,2-Ethanediamine reaction products with chlorinated iso-butylene
(Yes) (Yes)
84583 68 6 (Z)-4-Oxo-4-(tridecylamino)-2-butenoic acid (Maleic acid tri-decylamide)
(Yes) No
Polyolefin Mannich base (Yes) No
Table 13.2 Additive compounds used in Denmark where an added risk could not be excluded in the risk screening,
potentially due to lack of data.
A list of 5 additive compounds was established, see Table 13.2, where a preliminary risk as-signment could be reversed with additional information on water solubility and/or vapor pres-sure.
Finally, properties that may imply an added risk if incorporated in fuel additives and spilled were identified:
• High water solubility
• High vapor pressure
• Low biodegradability
• Human health or environmental hazard.
Avoiding these properties in designing new fuel additives would help avoiding added risk for soil, air and groundwater in case of spills.
33 (): the risk assignment is preliminary only and additional data are required.
92
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100
A P P E N D I X A
Examples of additive groups and fucntions34
34
References: /1-3;29-36/
101
Purpose Function Mechanism of func-
tion
Typical chemical structures Compound examples,
gasoline
Compound examples,
diesel
Antiknock Increase in octane number by inhibition of autoignition (knock)
Inhibition of fast free radical reactions
Previously primarily organic lead com-pounds, but other metalorganic com-pounds have been used as well (man-ganese and iron based). Now primarily oxygen rich organics such as ethers and alcohols. Alternatively branched hydrocarbon or aromatic fuel fractions. Suggested other heteroorganic com-pounds such (nitrogen, selenium or halogen based).
Tetraethyl lead Tetramethyl lead Ethyltrimethyl lead Diethyldimethyl lead Methyltriethyl lead Methylcyclopentadi-enylmangane tricar-bonyl Dicyclopentadienyl iron Methanol Ethanol Propanol Isopropanol Butanol 2-Butanol Isobutanol tert-Butanol Dimethylether Methyl-tert-butylether Ethyl-tert-butylether Diisopropylether tert-Amylether Isopropyl-tert-butylether sec-Butyl-tertbutylether tert-Butylacetate Acetylacetone 2,2,4-Trimethylpentane Aniline 3,4-Dimethylaniline N-Methylaniline 4-Methylaniline 3,5-Dimethylanaline
None35
35 None: additives for this purpose are not relevant for this fuel, or no additives have been listed for this purpose and this fuel in the references. 102
Purpose Function Mechanism of func-
tion
Typical chemical structures Compound examples,
gasoline
Compound examples,
diesel
N,N-Dimethylaniline 4-Ethylaniline 4-tert-Butylaniline
Inhibition of crystalliza-tion of water
Surfactants as salts and glycolesters of longchain carboxylic acids, amines, amides, imidazolines and phosphates.
Anti-icing Inhibition of ice forma-tion
Depression of water freezing point
Short chain alcohols, amides, amines, glycols and glycolethers.
Dimethylformamide 2-Propanol Dipropylenglycol
None
Antioxi-dants
Inhibition of fuel oxida-tion forming polymers (“gum”) Stabilization of lead additives
Inhibition of free radi-cal reactions
Aromatic amines and diamines, para-phenylendiamines. Sterically hindered alkylphenols, or-thoalkylated phenols, 2,6-dialkyl-phenols, 2,4,6-Trialkylphenols. Trialkylamines. Aminophenols.
N,N'-Di-sec-butyl-p-phenylenediamine N,N'-Di-isopropyl-p-phenylenediamine N,N'-Di-(1,4-dimethylpentyl)-p-phenylenediamine N,N'-Di-(1-methylheptyl)-p-phenylenediamine 4-Methyl-2,6-di-tert-butylphenol 2,6-Di-tert-butylphenol 2,4-Dimethyl-6-tert-butylphenol
2,4-Dimethyl-6-tert-butylphenol 2-Di-tert-butyl-4-methylphenol
Anti-corrosion
Inhibition of corrosion in engine, fuels lines, tanks and fuel pipe-lines
Formation of protective layer on metal sur-faces
Surfactants as longchain carboxylic acids, amides, phosphates and sul-phonates, often added as salts with organic amines. Zink dithiophosphates.
Acrylcarboxylates
None
Reduction of acidic corrosion
Alkaline compounds that neutralize acidic constituents
Alkylamines. Alkanolamine. Amides. Carboxylates.
None N,N-Dimethylcyclo-hexylamine
103
Purpose Function Mechanism of func-
tion
Typical chemical structures Compound examples,
gasoline
Compound examples,
diesel
Antifoa-ming
Inhibition of foam for-mation during pumping of the fuel
Dispersion of air bob-bles due to binding in surface layer between fuel and air
Polysiloxanes None None
Antistatic Inhibition of static elec-tricity and thus of spark formation and ignition of the fuel dur-ing handling
Increase in fuel electri-cal conductivity
Organometals (as chromium or cal-cium). Surfactants. Oxygenates. Sulphur and nitrogen containing poly-mers. Quarternary ammonium compounds. Alkylbenzenesulfonates. Carboxylates. carboxylic acids. Polyamides. Polyamines.
None Cr and Ca salts of mo-no- and dialkylsalicylic acid or dodecyl sulfo-succinic acid. High molecular weight polysulfones Toluene
Ash modi-fication
Inhibition of the effect of ash or impurities such as vanadium, sulphur and sodium
Increase of ash melt-ing or sinter point re-ducing coating Decrease in ash parti-cle size
Carboxylates. Phenols.
None Zink diaryl dithiophosphates
Deposit control
Reduction in formation of deposits from parti-cles
Disperse particles and prevent them from forming aggregates
Amides of longchain carboxylic acids and diamines. Amine carboxylic acids. Polyethers and polybutenes with polar
None None
104
Purpose Function Mechanism of func-
tion
Typical chemical structures Compound examples,
gasoline
Compound examples,
diesel
groups (succinimid, amine, diamine, amide or imidazoline). Longchain sulphonates. Mannich bases.
Biocides Prevention of microbial growth
Toxic to microorga-nisms
Organic boron compounds. Imines and amines. Imidazolines. Thiazines.
None None
Demulsi-fiers/ de-hazers
Removal of water droplets (dispersion)
Increase of fuel solu-bility of water by sur-factant action
Quaternary ammonium compounds. Alkoxylated polyglycols. Arylsulphonates. Other surfactants.
None None
Visible coloration of fuel
Azocompounds. Anthraquinones.
Alkylated azobenzene-4-azo-2-napthols 1-benzeneazo-2-naphthol 1,4-Diisopropylamino-anthraquinon N,N-Diethyl-4-(phenylazo)benzenamin
Dyes and markers
Identification of fuels sold with tax reduction or otherwise for spe-cific purposes
Identification of added markers using chemi-cal analysis
Diphenylamine Furfural 4-Hydroxybenzoic acid propyl ester
None
Flow improvers
Maintenance of flow properties of fuel be-low cloud point
Creation of large num-ber of small crystals preventing formation of large crystals
Copolymers of ethylene and vinylace-tate. Polyacrylates and –metacrylates. Polymers of alkenes and esters gener-
None Longchain polyesters of acetic acid and unsatu-rated C16 alcohols Polyolefine esters of 2-ethylhexylacrylate
105
Purpose Function Mechanism of func-
tion
Typical chemical structures Compound examples,
gasoline
Compound examples,
diesel
Inhibition of growth of crystals by binding to the surfaces
ally. Polyolefins. Chlorinated hydrocarbons.
Ethylen vinyl klorid co-polymers
Improving spark for-mation
Formation of coating in plug that enhances ignition
Organopotassium compounds None None Com-bustion catalysts
Reduction of soot for-mation
Prevention of cracking during combustion
Inorganic and organic metal com-pounds (as barium, calcium, cerium, iron, manganese, platinum, frequently carboxylates)
None Dicyclopentadienyliron Mn, MnO Mg, MgO, MgO2 Al2O3
Prevention of lead de-posits for leaded gaso-line
Formation of hydro-chloric acid that dis-solves/prevents lead deposits
Dihaloalkanes 1,2-Dibromoethane 1,2-Dichloroethane
None Lead sca-vengers
Easier removal of de-posits
Formation of friable lead borates that are mechanically removed
Glycolborates Cresylphosphates
Cresyldiphenylphospha-te Tri-ortho-cresylphosphate
None
Metal deactiva-tors
Prevention of fuel oxi-dation and “gum” for-mation
Complexation and thus deactivation of metal ions
Complex binders N,N’-Disalicylidene-1,2-diaminopropane
36
N,N-Disalicylidine-1,2-trans-cyclohexanediamine 1,2,3-Thiadiazol N,N-Disalicylidineethyl-enediamine 1,2,3-Benzotriazol 2-Mercapto-1,3-benzothiazol 2-Mercaptobenzimidazol
N,N’-Disalicylidene-1,2-diaminopropane
36 Most commonly applied metal deactivator in the fuel industry /112/. 106
Purpose Function Mechanism of func-
tion
Typical chemical structures Compound examples,
gasoline
Compound examples,
diesel
Increase in octane number by inhibition of autoignition (knock)
Inhibition of fast free radical reactions
Oxygena-tes
Reduction in VOC emission
Improved combustion of fuel
Shortchain, aliphatic alcohols and ethers
Methanol Ethanol Propanol Isopropanol Butanol 2-Butanol Isobutanol tert-Butanol Dimethylether Methyl-tert-butylether Ethyl-tert-butylether Diisopropylether tert-Amylether Isopropyl-tert-butylether sec-Butyl-tertbutylether Acetylacetone
None
Odorants Reduction of unplea-sant odour
Adds “pleasant” odour None None Vanilin
Prevention of valve seat recession
Formation of protective layer on metal sur-faces
Alkyl leads Sodium naphtenates (sodium salts of cyclopentanecarbocylic acids) Organic potassium and aminophos-phate compounds
Tetraethyl lead Tetramethyl lead MMT
None Anti-wear
Prevention of wear from low viscosity fuels
Formation of protective layer on metal sur-faces
Polyfunctional organic acids, see also lubricants
None Polyesters
Lubricants Reduction of friction and thus prevention of engine wear
Formation of protective layer on metal sur-faces Protection of protective layer in combustion chamber
High boiling petroleum fractions. Alicyclic compounds, cycloalkane des-tillates. Longchain, polar organic compounds Surfactants. Organic lead and molybdenum com-
None Phosphate ester amide neutralized with long-chain amine
107
Purpose Function Mechanism of func-
tion
Typical chemical structures Compound examples,
gasoline
Compound examples,
diesel
pounds. Zink dithiophosphates. Dialkylphosphates and –hydrogenphosphates.
Spray en-hancers
Improvement of fuel distribution
Formation of layer in injector that supports formation of small droplets
Quaternary ammonium compounds and other surfactants
None None
Cetane improvers
Enhancement of igni-tion and combustion
Formation of free radi-cals for initiation of ignition
Organic nitrates, nitrites, peroxides, nitro and nitroso compounds
None Isopropylnitrate Isoamylnitrate Isohexylnitrate Cyclohexylnitrate 2-Ethylhexylnitrate 2-Butoxyethylnitrate 3-Tetrahydrofurylnitrate 4-Morphoneethylnitrate Cyclodeceylnitrate 5-Propyl-1,2,3,4-tetraazocyclopentadi-ene 2,2-Di-thio-di-isobutyraldehyde 2-Methyl-2-nitro-1-propylnitrate Tetraethylenglycoldini-trate Triethylenglycoldinitrate Diethylenglycoldinitrate
Different purposes
Depending upon pur-pose
Depending upon func-tion
Surfactants Polar units: Amines Amides Polyglycol esters Aminohydroxyamides Imidaziolines
Polar units: Alcohols Amines Amides Alkylphenols Carboxylic acids
108
Purpose Function Mechanism of func-
tion
Typical chemical structures Compound examples,
gasoline
Compound examples,
diesel
Succinimides Phosphate
Sulfonates Imidaziolines Succinimides
Polymers None Styrene/ester copoly-mers
109
110
A P P E N D I X B
Danish use of potential additives 2001 and their classifications
111
CAS number Compound Danish 2001 use in t from the SPIN database Classifications in the Danish Product Register
Total use
Produc-tion of fuels
Fuel addi-tives
Comments Health37 Envi-ron-ment
38
Comments
50 00 0 Formaldehyde 459 039 0 - T - - 57 55 6 1,2-Propanediol 10559 0 - - Xi - - 62 53 3 Aniline 0,8 - - - T N - 64 17 5 Ethanol 16587 0,2 - - - - - 67 56 1 Methanol 9201 1,8 - - T - - 67 63 0 2-Propanol 19031 14 15 - Xi - - 68 12 2 Dimethyl formamide 78 - - - T - - 75 21 8 Ethylene oxide 12 0 0 - T - - 75 56 9 Propylene oxide 14 0 0 - T - - 75 65 0 t-Butyl alcohol 6,1 - - - Xn - - 75 74 1 Tetramethyllead conf conf conf - Tx N - 78 00 2 Tetraethyl lead - - - - Tx N - 78 31 9 Phosphoric acid 4-
methylphenyl diphenyl ester (Cresyldiphenylphosphate)
- - - - - - -
78 83 1 2-Methyl-1-propanol 2102 - - - Xi - - 78 92 2 sec-Butyl alcohol 50 - - - Xi - - 78 93 3 Methyl ethyl ketone 1668 - - Used in S as fuel
additive Xi - -
81 15 2 2,4,6-Trinitro-1,3-dimethyl-5-tert-butylbenzene
0,1 - 0 - - - -
85 83 6 Azobenzene-4-azo-2-naphtol (Sudan IV)
0,1 - - Registered in S for fuel production
Xn - -
94 91 7 2,2'-[(1-Methyl-1,2- 2,1 - 0 2000 1.4 t regis- Xn - -
37 Tx: very toxic, T: toxic, Xn: harmful, C: corrosive, Xi: irritant 38 N: very environmentally hazardous 39 0: the compound has been registered for the purpose but no use was registered in 2001 112
CAS number Compound Danish 2001 use in t from the SPIN database Classifications in the Danish Product Register
Total use
Produc-tion of fuels
Fuel addi-tives
Comments Health37 Envi-ron-ment
38
Comments
ethanediyl)bis(nitrilomethylidyne)]-bis-phenol (N,N-Disalicylidine-1,2-propandiamine)
tered in DK as fuel additive
94 93 9 2,2'-[1,2-Ethanediyl-bis(nitrilomethylidyne)]-bis-phenol (N,N-Disalicylidinethylenedia-mine)
- - - Not registrered - - -
95 14 7 Benzotriazole 20 - - Corrosion inhibi-tor
Xn - -
95 64 7 3,4-Dimethylaniline conf conf conf - - - - 98 94 2 N,N-
Dimethylcyclohexylamine 117 - - - C N -
100 61 8 Monomethylaniline 0,1 - - - T N - 101 96 2 N,N'-Di-sec-butyl-4-
phenylenediamine conf conf conf - - - -
102 54 5 Bis-cyclopentadienyliron 1,4 - - Registrered in S for fuel production
Xn - -
102 71 6 Triethanolamine 1065 99 - - Xi - - 104 76 7 2-Ethyl-1-hexanol 641 472 440 - Xi - - 105 58 8 Diethyl carbonate conf conf conf - - - - 106 49 0 4-Methylaniline (para-
Toluidine) 0 - - - T N -
106 89 8 Epichlorohydrin (Chlor-methyloxirane)
9,8 0 - - T - -
106 93 4 1,2-Dibromoethane (Ethyl-ene dibromide)
conf conf conf - T N -
107 06 2 1,2-Dichloroethane (Ethyl- 0,3 - - - T - - 113
CAS number Compound Danish 2001 use in t from the SPIN database Classifications in the Danish Product Register
Total use
Produc-tion of fuels
Fuel addi-tives
Comments Health37 Envi-ron-ment
38
Comments
ene dichloride) 107 15 3 1,2-Diaminoethane (Ethyl-
enediamine) 7,8 - - - C - -
107 39 1 2,4,4-Trimethyl-1-pentene conf conf conf - - N - 107 40 4 2,4,4-Trimethyl-2-pentene conf conf conf - - - - 107 98 2 1-Methoxy-2-propanol (Pro-
pylene glycol monomethyl ether)
2524 0,9 - - - - -
108 20 3 Diisopropyl ether 0,1 - - - - - - 108 69 0 3,5-Dimethylaniline (3,5-
Xylidine) conf conf conf - - - -
108 95 2 Phenol 3158 4 - - T - - 109 86 4 2-Methoxyethanol 12 - - - T - - 110 05 4 Di-tert-Butylperoxide 3,6 - - - - - - 110 16 7 Maleic acid 121 0,5 - - Xn - - 110 25 8 (Z)-N-Methyl-N-(1-oxo-9-
octadecenyl)glycine (Oleoyl sarcosine)
22 - - 0.01 t registered for fuel use as
maximum 1992-2002
- - -
110 91 8 Morpholine 100 - - 0.02 t registered for fuel use as
maximum 2000-2002
C -
111 22 8 2,2'-[Ethane-1,2-diylbis(oxy)]bis ethyl dini-trate (Triethyleneglycoldini-trate)
- - - Not registrered - - -
111 40 0 N-(2-Aminoethyl)-1,2-ethane diamine (Diethyl-enetriamine)
50 - - - C - -
114
CAS number Compound Danish 2001 use in t from the SPIN database Classifications in the Danish Product Register
Total use
Produc-tion of fuels
Fuel addi-tives
Comments Health37 Envi-ron-ment
38
Comments
111 41 1 N-(2-Hydroxyethyl)ethylene-diamine (2-[(2-Aminoethyl)amino]ethanol)
2,8 - - - Xi - -
111 42 2 Diethanolamine 16475 6,1 - - Xn - - 111 76 2 2-Butoxy ethanol 869 29 - - Xn - - 112 24 3 N,N’-Bis-(2-aminoethyl)-1,2-
ethandiamine (Triethylene-tetramine)
55 - - - C - -
112 57 2 N- (2-aminoethyl)-N'-{2- (2-aminoethyl)amino}ethyl}-1,2-ethanediamine (Tetra-ethylenepentamine)
15 0,3 - - C N -
112 80 1 9-Octadecensyre (Oleic acid)
132 0,7 - - Xi - -
115 11 7 2-Methyl-1-propene (iso-Butylene)
0 - 0 - - - -
117 81 7 Di-sec-octyl phthalate (Dioctylphthalate)
3336 - - - T - -
121 33 5 4-Hydroxy-3-methoxybenzaldehyd (Va-nillin)
0,5 - - - Xn - -
121 69 7 N,N-Dimethylbenzenamine (N,N-Dimethylaniline)
0,6 - - - T N -
123 54 6 2,4-Pentanedione (Acety-lacetone)
5,7 - - - Xn - -
128 37 0 2,6-bis-(1,1-Dimethylethyl)-4-methylphenol (2,6-Di-tert-butyl-p-cresol)
299 0,1 - - Xn - -
128 39 2 2,6-bis-(1,1-Dimethylethyl)phenol (2,6-
136 - 133 - Xi - -
115
CAS number Compound Danish 2001 use in t from the SPIN database Classifications in the Danish Product Register
Total use
Produc-tion of fuels
Fuel addi-tives
Comments Health37 Envi-ron-ment
38
Comments
Di-tert-butyl-p-phenol) 129 39 2 2-(1,1-dimethylethyl)-4-
methylphenol (2-tert-Butyl-p-cresol)
0 - - - C - -
140 31 8 1-(2-Aminoethyl)piperazine (N-Aminoethylpiperazine)
36 - - - C - -
149 30 4 2-Benzothiazolethiol 6,4 - - - Xi N - 149 57 5 2-Ethylhexanoic acid 28 - - - Xn - - 513 85 9 2,3-Butanediol - - - Not registrered - - - 540 88 5 tert-Butyl acetate - - - Registered as
Texaco Lead Ap-preciator
- - -
541 02 6 Decamethylcyclopentasi-loxane
38 - - Used in N as fuel additive
- - -
543 87 3 Iso-pentyl nitrate (Iso-amyl nitrate)
- - - Not registrered Xi - -
556 67 2 Octamethylcyclotetrasilox-ane
36 - - Used in N as fuel additive
Xn - -
583 39 1 Benzimidazole-2-thiol conf conf conf - - - - 589 16 2 4-Ethylbenzenamine (4-
Ethylaniline) - - - Not registrered T - -
600 22 6 Methyl pyruvate - - - Not registrered - - - 616 38 6 Dimethyl carbonate conf conf conf conf - - - 623 53 0 Ethyl methyl carbonate - - - Not registrered - - - 637 92 3 Ethyl tert-butyl ether - - - Not registrered - - - 693 21 0 2,2'-Oxydiethanoldinitrate
(Diethylene glycol dinitrate) - - - Registrered for
use in S Tx - -
769 92 6 4-tert-butylaniline - - - Not registrered - - - 842 07 9 Benzene-azo-2-naphtol
(Sudan I) 6,9 - - - Xn - -
116
CAS number Compound Danish 2001 use in t from the SPIN database Classifications in the Danish Product Register
Total use
Produc-tion of fuels
Fuel addi-tives
Comments Health37 Envi-ron-ment
38
Comments
872 50 4 1-Methyl-2-pyrrolidinone 646 0,1 - - Xi - - 994 05 8 2-Methoxy-2-methylbutane
(tert-amyl methyl ether) - - - Not registrered - - -
1330 78 5 Tris(methylphenyl) phos-phate (Tricresyl phosphate)
1,0 - - - - - -
1634 04 4 Methyl tert-butyl ether, Tert-butyl methyl ether
conf conf conf conf - - -
1712 64 7 iso-Propyl nitrate - - - Not registrered Xi - - 1762 26 1 Trimethylethyl lead - - - Not registrered - - - 1762 27 2 Diethyldimethyl lead - - - Not registrered - - - 1762 28 3 Methyltriethyl Lead - - - Not registrered - - - 1879 09 0 2,4-Dimethyl-6-tert-
butylphenol 0,2 - - - Xn - -
2108 66 9 Cyclohexyl nitrate - - - Not registrered - - - 2481 94 9 N,N-Diethyl-4-
(phenylazo)benzenamine 0,1 - - - - - -
2682 20 4 2-Methyl-4-Isothiazolin-3-one
4,9 0 - - C - -
4525 33 1 Dimethyldicarbonate conf40 conf conf - - - - 5131 66 8 1-Butoxy-2-propanol 39 - - - Xi - - 6531 38 0 N,N'-Di-(2-
aminoethyl)piperazine conf conf conf - - - -
7491 09 0 Potassium 1,2-bis(2-ethylhexyloxycar-bonyl)ethanesulphonate
conf conf conf Use in S and N as fuel additive
with 10-15 t each
- - -
9003 27 4 Poly(iso-butylene) 159 - - - - - - 9003 28 5 Polybutene 52 - - - - - - 9003 29 6 Butene, homopolymer 85 - 3 - - - -
40
conf means, that the information is not accessible because of confidentially agreements with the additive producers/importers. 117
CAS number Compound Danish 2001 use in t from the SPIN database Classifications in the Danish Product Register
Total use
Produc-tion of fuels
Fuel addi-tives
Comments Health37 Envi-ron-ment
38
Comments
12108
13 3 Methyl cyclopentadienyl manganese tricarbonyl, MMT
conf conf conf conf T - -
13463
39 3 Nickel Carbonyl - - - Only conf data for SF
Tx N -
13463
40 6 Iron Pentacarbonyl - - - Only conf data for SF
Tx - -
14233
37 5 1,4-bis-(iso-Propylamino)anthraquinone
0 - - - - - -
16153
75 6 N-(1-Methylethyl)benzene-1,4-diamine
- - - Not registrered - - -
20633
11 8 Hexyl nitrate - - - Not registrered - - -
22464
99 9 Zirconium 2-ethylhexanoate 99 - - - - - -
24028
46 4 N-[2-(1-piperazinyl)ethyl]-1,2ethanediamine
0,5 - - - - - -
24937
96 7 Ethenevinylacetat copoly-mer
- - - Not registrered - - -
25068
38 6 4,4’-(1-Methylethyliden)-bis-phenol polymer with chlor-methyloxirane (Bisphenol A epichlorhydrin copolymer, Epon 1001 Resin)
4953 9,6 - - Xi N -
25265
71 8 Dipropylene glycol 1047 - - - - - -
25265
76 3 Phenylenediamine (mixed isomers)
conf conf conf - - - -
26172
55 4 5-Chloro-2-Methyl-4-Isothiazolin-3-One
10 0 - - C - -
118
CAS number Compound Danish 2001 use in t from the SPIN database Classifications in the Danish Product Register
Total use
Produc-tion of fuels
Fuel addi-tives
Comments Health37 Envi-ron-ment
38
Comments
26447
24 5 1,2,3,4-Tetrahydro-1-hydroperoxynaphthalene (Tetralinhydroperoxide)
- - - Not registrered C N -
27193
86 8 Dodecylphenol 2,9 - 0 - - - -
27247
96 7 2-Ethylhexyl nitrate 3925 - 1501 - Xi - -
29385
43 1 5-Methyl-1,2,3-benzotriazole (Tolyltriazole)
30 - - Corrosion inhibi-tor, registered for
fuel use
Xn - -
31295
46 2 4-(2-Aminoethyl)-N- (2-aminoethyl)-N'-{2- {(2-aminoethyl)amino}ethyl}-1,2-ethanediamine (N,N,N'-tris(2-amino-ethyl)ethylenediamine)
- - - Not registrered - - -
31295
49 5 N-(2-aminoethyl)-N'-[2-(1-piperaz-inyl)ethyl]ethylenediamine
conf conf Conf - - - -
31295
54 2 N-(2-aminoethyl)piperazine-1,4-diethylamine
conf conf Conf S use 127 t i 2000
- - -
36484
54 5 Bisphenol-A reacted with propylenoxide or chlorpro-pylenoxide
4,1 - 0 - - - -
53040
75 8 Dodecylphenol-poly(methyl)ethoxylate
1,8 - 1 - - - -
61788
89 4 Fatty acids, C18-unsatd., dimers
34 - 0 - - - -
6179 12 3 Tall Oil Fatty Acids 3493 3237 - - - - - 119
CAS number Compound Danish 2001 use in t from the SPIN database Classifications in the Danish Product Register
Total use
Produc-tion of fuels
Fuel addi-tives
Comments Health37 Envi-ron-ment
38
Comments
0 61791
44 4 N-Tallow-2,2’-imino bis-ethanol
5,6 - - Fuel additive in S - - -
63428
91 1 Formaldehyde reacted with 4-(1,1-dimethylpropyl)phenol, pro-pyleneoxide and ethylene-oxide
2,7 - 0 - - - -
68123
18 2 Bisphenol-A reacted with ethyleneoxide, propyleneox-ide or chloropropyleneoxide
58 - 53 Fuel additive in N - - -
68411
46 1 Benzenamine, N-phenyl-, reaction products with 2,4,4-trimethylpentene
0,6 - - - - N -
68439
80 5 Polyethylenpolyamines re-acted with polybutenyl suc-cinic anhydride
85 - 0 In S used for fuel production
- - -
68891
84 9 1,2-Ethanediamine, reaction products with chlorinated isobutylene homopolymer
55 - - 0.22 t registered for fuel use as
maximum 1995-2002
- - -
68920
94 5 Polymers of alkylated imi-dazolamine with polyethyl-ene
- - - Fuel additive in S - - -
68955
53 3 C12-C14 Tertiæry amines (Primene)
1,2 - - Fuel additive in S - - -
73513
43 6 iso-Octylnitrate - - - Not registrered - - -
84583
68 6 (Z)-4-Oxo-4-(tridecylamino)-2-butenoic acid (Maleic acid
263 261 7 - - - -
120
CAS number Compound Danish 2001 use in t from the SPIN database Classifications in the Danish Product Register
Total use
Produc-tion of fuels
Fuel addi-tives
Comments Health37 Envi-ron-ment
38
Comments
tridecylamide) 84605
20 9 Polyethylenpolyamines re-acted with polyisobytenyl succinic anhydride
1317 - 509 - - - -
85203
90 3 ar-Styrenated 1-[[2-methyl-4-[(2-methyl-phenyl)azo]phenyl]azo]-2-naphthalenol (Azobenzene-4-azo-2-naphtols)
- - - Not registrered - - -
92257
31 3 ar-Heptyl ar',ar''-Me 2-1-[[4-(phenylazo)phenyl]azo]-naphthalenol (Azobenzene-4-azo-2-naphtols)
0 - - - - - -
98761
78 5 N,N-Dimethyl-1,3-diaminopropane reacted with chlorinated polyisobu-tylene
- - - Fuel additive in S - - -
121
122
A P P E N D I X C
Physical-chemical data of potential additives41
41 References: /94-97/
123
CAS number Compound pka log Kow H S
(-) mg/L 50 00 0 Formaldehyde 0,35 1,39E-05 400000 52 51 7 2-Bromo-2-nitropropane-
1,3-diol -0,64 4,66E-10 62900
56 81 5 Glycerol 14,4 -1,76 7,15E-10 1220000 57 13 6 Urea 0,1 -2,11 7,11E-11 545000 57 55 6 1,2-Propandiol 14,8 -0,92 5,35E-09 Blandbar 60 12 8 2-Phenylethanol 1,36 6,13E-06 16000 64 02 8 Tetrasodium ethylenedia-
minetetraacetate 500000
64 17 5 Ethanol 15,9 -0,31 2,57E-04 Blandbar 67 56 1 Methanol 15,3 -0,77 0,00018 Blandbar 67 63 0 2-Propanol 17,8 0,28 0,000307 1000000 75 21 8 Ethylene Oxide -0,3 0,006049 Blandbar 75 56 9 Propylene oxide 0,03 0,002845 590000 75 65 0 t-Butyl Alcohol 19,2 0,35 0,00037 1000000 77 92 9 Citric acid 3,13
4,76 6,40
-1,72 3,39E-16 590000
78 93 3 Methyl ethyl ketone 0,29 0,001921 353000 81 15 2 2,4,6-Trinitro-1,3-dimethyl-
5-tert-butylbenzene 4,45 3,16E-07 0,821
91 64 5 2H-1-Benzopyran-2-on (Coumarin)
1,39 0,000284 2500
95 14 7 Benzotriazole 8,37 1,44 1,3E-05 19800 102 54 5 bis-Cyclopentadienyliron 3,28 81 102 71 6 Triethanolamine 7,76 -1,59 4,09E-06 Blandbar 104 76 7 2-Ethyl-1-hexanol 0,001083 880 105 58 8 Diethyl carbonate 1,21 0,003638 18800 106 93 4 1,2-Dibromoethane (Ethyl-
ene dibromide) 1,96 0,026568 3910
107 06 2 1,2-Dichloroethane (Ethyl-ene dichloride)
1,48 0,048231 8600
107 21 1 1,2-Ethanediol (Ethylene -1,36 2,45E-06 Blandbar
124
CAS number Compound pka log Kow H S
(-) mg/L glycol)
107 39 1 2,4,4-Trimethyl-1-pentene 4,55 30,65504 107 40 4 2,4,4-Trimethyl-2-pentene 4 36,00945 107 64 2 Dimethyldioctadecylammo-
nium chloride (Di(hardened tallow)dimethylammonium chloride, Distearyldimethyl-ammonium chloride)
3,8 2,62E-06
108 20 3 Diisopropyl ether 1,52 0,094009 8800 108 95 2 Phenol 9,89 1,46 1,36E-05 93000 109 86 4 2-Methoxyethanol -0,77 1,35E-05 1000000 110 25 8 (Z)-N-Methyl-N-(1-oxo-9-
octadecenyl)glycine (Oleoyl sarcosine)
6,83 2,68E-08 0,19
111 42 2 Diethanolamine 8,88 -1,13 1,59E-09 111 76 2 2-Butoxy ethanol 0,83 8,17E-07 1000000 112 34 5 2-(2-Butoxyethoxy)ethanol 0,56 0,000217 1000000 112 80 1 9-Octadecensyre (Oleic
acid) 5,02 7,73 0,001839
115 11 7 2-Methyl-1-propene (iso-Butylene)
2,34 8,910397 263
117 81 7 Di-sec-octyl phthalate (Dioctylphthalate)
7,6 5,31E-06 0,29
128 39 2 2,6-bis(1,1-Dimethylethyl)phenol (2-tert-Butyl-p-cresol)
4,92 0,000129 2,5
138 86 3 1-Methyl-4-(1-methyl-ethenyl)cyclohexen (Limo-nene)
4,23 15,53189 13,8
149 57 5 2-Ethylhexanoic acid 2,64 0,000119 1400 513 85 9 2,3-Butanediol 14,9 -0,92 8,26E-05 Blandbar 532 32 1 Sodium benzoate -2,27 4,46E-06 55000 541 02 6 Decamethylcyclopentasi- 5,2 16,34935 0,24
125
CAS number Compound pka log Kow H S
(-) mg/L loxane
556 67 2 Octamethylcyclotetrasilox-ane
17,16682 0,05
600 22 6 Methyl pyruvate -0,96 2,86E-05 760000 616 38 6 Dimethyl carbonate 0,23 0,025341 85000 637 92 3 Ethyl tert-butyl ether 1,92 0,057223 12000 994 05 8 2-Methoxy-2methylbutane
(tert-amyl methyl ether) 1,92 0,110358
1634 04 4 Methyl tert-butyl ether, Tert-butyl methyl ether
0,94 0,023993 51000
2634 33 5 1,2-Benzisothiazolin-3-one 0,64 2,83E-07 21400 2650 18 2 Diammonium-N-ethyl-N-[4-
[[4-[ethyl[(3-sulfophenyl)me-thyl]amino]phenyl](2-sulfophenyl)methylen]-2,5-cyclohexadien-1-yliden]-3-sulfobenzen methanamini-umhydroxid (Acid Blue 9)
-1,5 4,66E-42 1,45
2682 20 4 2-Methyl-4-isothiazolin-3-one
-0,83 2,04E-06 537000
4525 33 1 Dimethyldicarbonate -0,86 0,01823 5131 66 8 1-Butoxy-2-propanol 0,98 5,31E-06 42000 7491 09 0 Potassium 1,2-bis(2-
ethylhexyloxycar-bonyl)ethanesulphonate
6,10 2,04E-10
8000 41 7 Terpene alcohol 3,28 0,000499 1980 9016 45 9 Nonylphenolpolyethoxylater
(Tergitol NP-33) 1,68E-10
12108
13 3 Methyl cyclopentadienyl manganese tricarbonyl, MMT
3,7 4,00E-07 29
20633
11 8 Hexyl nitrate 3,21 0,060901 110
2246 99 9 Zirconium 2-ethylhexanoate 4,37 0,78 126
CAS number Compound pka log Kow H S
(-) mg/L 4 25377
73 5 3-(Dodecenyl)dihydro-2,5-furandion (Dodecenylsuc-cinic anhydride)
6,41 0,016922 0,064
26172
55 4 5-Chloro-2-methyl-4-isothiazolin-3-one
-0,34 1,46E-06 15000
26447
24 5 1,2,3,4-Tetrahydro-1-hydroperoxynaphthalene (Tetralinhydroperoxid)
2,63 1,92E-05 370
27193
86 8 Dodecylphenol 6,58 0,001414
27247
96 7 2-Ethylhexyl nitrate 4,12 0,058858 5,361
29385
43 1 5-Methyl-1,2,3-benzotriazole (Tolyltriazole)
1,71 6,62E-06 3069
34590
94 8 (2-Methoxy-methylethoxy)propanol (Dipropylene glycol methyl ether)
-0,35 4,7E-08 Blandbar
84583
68 6 (Z)-4-Oxo-4-(tridecylamino)-2-butenoic acid (Maleic acid tridecylamide)
5,75 7,36E-11
127
128
A P P E N D I X D
Distribution of potential additives between soil, air and water
129
The distribution modelling was in principle based upon the distribution model used in risk assessment of contaminated sites in Denmark /97;98/.
Henrys Law was used to describe the distribution of a compound between air and water e.g.:
w
a
C
CH =
where H is the Henrys constant (-), Ca is the concentration in air (mg/L), and Cw is the concentration in water (mg/L).
The distribution of a compound between water and soil is described by the following equation:
w
s
dC
CK =
where Kd is the sorption distribution constant (L/kg), Cs is the concentration in soil (mg/kg), and Cw is the concentration in water (mg/L).
The total concentration at the beginning distribute after the mass balance, when there is no free phase:
where CT is total concentration in the bulk soil (mg/kg dry matter, dm), C with index a, w or s is the concentration in air, water and soil, Va is the volume of air, Vw is the vol-ume of water, and M is the amount of soil.
Kd was estimated based on the content of organic matter foc (-) and the octanol water distribution coefficient Kow (L/kg) using the equation:
84.0)log()log(04.1)log( −+= ocowd fKK
The calculations have been performed on two different soils with the properties:
Topsoil
Air volume 0.1 L
Water volume 0.35 L
Amount of soil 1.43 kg
Content of organic carbon 0.02
Density of soil 2.6 kg/L
Subsoil
Air volume 0.1 L
Water volume 0.30 L
Amount of soil 1.62 kg
Content of organic carbon 0.001
Density of soil 2.7 kg/L
MCVCVCMC swwaaT ++=
130
CAS number Compound Topsoil, 2 % organic matter Subsoil, 0,1 % organic matter
Water Air Soil Water Air Soil 50 00 0 Formaldehyde 97 0 2,7 100 0,03 0,3 52 51 7 2-Bromo-2-nitropropane-
1,3-diol 100 0 0,3 100 0 0,03
56 81 5 Glycerol 100 0 0,02 100 0 0 57 13 6 Urea 100 0 0,01 100 0 0 57 55 6 1,2-Propandiol 100 0 0,1 100 0 0,02 60 12 8 2-Phenylethanol 77 0 24 96 0 3,5 64 17 5 Ethanol 99 0,01 0,6 100 0,1 0,07 67 56 1 Methanol 100 0,01 0,2 100 0,04 0,02 67 63 0 2-Propanol 98 0,01 2,3 100 0,06 0,3 75 21 8 Ethylene Oxide 99 0,2 0,6 99 1,2 0,06 75 56 9 Propylene oxide 99 0,1 1,3 99 0,6 0,2 75 65 0 t-Butyl Alcohol 97 0,01 2,7 100 0,1 0,3 77 92 9 Citric acid 100 0 0,02 100 0 0 78 93 3 Methyl ethyl ketone 98 0,1 2,3 99 0,4 0,3 81 15 2 2,4,6-Trinitro-1,3-dimethyl-
5-tert-butylbenzene 0,2 0 100 1,6 0 98
91 64 5 2H-1-Benzopyran-2-on (Coumarin)
75 0,01 25 96 0,05 3,8
95 14 7 Benzotriazole 73 0 27 96 0 4,2 102 54 5 bis-Cyclopentadienyliron 3,2 0 96 22 0 78 102 71 6 Triethanolamine 100 0 0 100 0 0 104 76 7 2-Ethyl-1-hexanol 10 0 90 49 0,1 50 105 58 8 Diethyl carbonate 82 0,1 18 97 0,1 2,5 106 93 4 1,2-Dibromoethane (Ethyl-
ene dibromide) 44 0,3 56 83 4,4 13
107 06 2 1,2-Dichloroethane (Ethyl-ene dichloride)
70 1 29 87 8,4 4,2
107 21 1 1,2-Ethanediol (Ethylene glycol)
100 0 0,1 100 0 0
107 39 1 2,4,4-Trimethyl-1-pentene 0,1 1,4 98 0,7 44 56 107 40 4 2,4,4-Trimethyl-2-pentene 0,6 5,7 94 1,1 77 22
131
CAS number Compound Topsoil, 2 % organic matter Subsoil, 0,1 % organic matter
Water Air Soil Water Air Soil 107 64 2 Dimethyldioctadecylammo-
nium chloride (Di(hardened tallow)dimethylammonium chloride, Distearyldimethyl-ammonium chloride)
0,9 0 99 7,4 0 93
108 20 3 Diisopropyl ether 68 1,8 30 80 15 4,3 108 95 2 Phenol 72 0 28 96 0 4,4 109 86 4 2-Methoxyethanol 100 0 0,2 100 0 0,02 110 25 8 (Z)-N-Methyl-N-(1-oxo-9-
octadecenyl)glycine (Oleoyl sarcosine)
0 0 100 0,01 0 100
111 42 2 Diethanolamine 100 0 0,1 100 0 0,01 111 76 2 2-Butoxy ethanol 92 0 8 99 0 1,0 112 34 5 2-(2-Butoxyethoxy)ethanol 96 0,01 4,3 99 0,04 0,5 112 80 1 9-Octadecensyre (Oleic
acid) 0 0 100 0 0 100
115 11 7 2-Methyl-1-propene (iso-Butylene)
15 38 47 5,2 92 2,0
117 81 7 Di-sec-octyl phthalate (Dioctylphthalate)
0 0 100 0 0 100
128 39 2 2,6-bis(1,1-Dimethylethyl)phenol (2-tert-Butyl-p-cresol)
0,1 0 100 0,5 0 99
138 86 3 1-Methyl-4-(1-methyl-ethenyl)cyclohexen (Limo-nene)
0,3 1,5 98 1,5 46 52
149 57 5 2-Ethylhexanoic acid 13 0 87 56 0,01 44 513 85 9 2,3-Butanediol 100 0 0,1 100 0,02 0,02 532 32 1 Sodium benzoate 100 0 0,01 100 0 0 541 02 6 Decamethylcyclopentasi-
loxane 0,03 0,2 100 3,0 97 0
556 67 2 Octamethylcyclotetrasilox-ane
0,04 0,2 100 0,3 11 89
600 22 6 Methyl pyruvate 100 0 0,1 100 0,01 0,01 132
CAS number Compound Topsoil, 2 % organic matter Subsoil, 0,1 % organic matter
Water Air Soil Water Air Soil 616 38 6 Dimethyl carbonate 97 0,7 2 95 4,8 0,2 637 92 3 Ethyl tert-butyl ether 46 0,8 54 80 9,1 11 994 05 8 2-Methoxy-2methylbutane
(tert-amyl methyl ether) 45 1,4 53 74 16 10
1634 04 4 Methyl tert-butyl ether, Tert-butyl methyl ether
89 0,6 10 94 4,5 1,3
2634 33 5 1,2-Benzisothiazolin-3-one 95 0 5,2 99 0 0,5 2650 18 2 Diammonium-N-ethyl-N-[4-
[[4-[ethyl[(3-sulfophenyl)me-thyl]amino]phenyl](2-sulfophenyl)methylen]-2,5-cyclohexadien-1-yliden]-3-sulfobenzen methanamini-umhydroxid (Acid Blue 9)
100 0 0,03 100 0 0
2682 20 4 2-Methyl-4-isothiazolin-3-one
100 0 0,2 100 0 0,02
4525 33 1 Dimethyldicarbonate 99 0,5 0,2 96 3,5 0,02 5131 66 8 1-Butoxy-2-propanol 89 0 11 99 0,001 1,4 8000 41 7 Potassium 1,2-bis(2-
ethylhexyloxycar-bonyl)ethanesulphonate
3,2 0 97 22 0,02 78
9016 45 9 Terpene alcohol 67 0 33 100 0 0,1 12108
13 3 Nonylphenolpolyethoxylater (Tergitol NP-33)
9,2 0 91
20633
11 8 Hexyl nitrate 3,8 0,1 96 24 2,9 73
25377
73 5 3-(Dodecenyl)dihydro-2,5-furandion (Dodecenylsuc-cinic anhydride)
0 0 100 0,02 0 100
26172
55 4 5-Chloro-2-methyl-4-isothiazolin-3-one
99 0 0,5 100 0 0,1
26447
24 5 1,2,3,4-Tetrahydro-1-hydroperoxynaphthalene (Tetralinhydroperoxid)
13 0 87 57 0 43
133
CAS number Compound Topsoil, 2 % organic matter Subsoil, 0,1 % organic matter
Water Air Soil Water Air Soil 27193
86 8 Dodecylphenol 0 0 100 0,01 0 100
27247
96 7 2-Ethylhexyl nitrate 0,4 0,01 100 3,5 0,4 96
34590
94 8 (2-Methoxy-methylethoxy)propanol (Dipropylene glycol methyl ether)
99 0 0,5 100 0 0,06
84583
68 6 (Z)-4-Oxo-4-(tridecylamino)-2-butenoic acid (Maleic acid tridecylamide)
0,01 (41)42 0 (0) 100 (59) 0,08 (86) 0 (0) 100 (14)
42 Calculated for the ionized compound in brackets. 134
A P P E N D I X E
Template for confidentiality agreement with the 5 Danish petro-leum companies
135
Confidentiality agreement This agreement is made in duplicate on November 26th 2003 between: Company, address hereafter called the company and: DHI Water & Environment, Agern Alle 5, DK-2970 Hørsholm, Denmark hereafter called DHI. The company and DHI has agreed on the following: The company will make safety data sheets available to DHI for all additives43 and additive mix-tures added to gasoline and diesel distributed in Denmark by the company. In addition, data on concentrations in different products and on amounts used annually in Denmark will be made available for all additives and additive mixtures. Likewise, the company will make safety data sheets available for DHI on all additives and addi-tive mixtures added to raw gasoline and diesel (distributed in Denmark) by the company’s sup-plier of raw products. In addition, data on concentrations in different products and on amounts used annually for products distributed in Denmark will be made available for all additives and additive mixtures. DHI will keep all information confidential with access only by Christian Grøn, and the information will be stored separately under lock in the DHI alarm protected safe area used for storage of other strictly confidential information. DHI will review the safety data sheets and will if relevant request additional information on com-ponents not specified in the data sheets and further on toxicity, physical-chemical properties and persistence. The company will make the additional information available to DHI directly or by establishing a contact between DHI and the company’s supplier of additives or raw products. DHI will review the environmental and human health risks potentially associated with the addi-tives and produce a list of high risk44 additives and their properties, if any such additives are identified. The information on high risk additives can be published in a report to the Danish cli-ent that will be made available to the public. Information on all other, non risk additives will only be published in generic terms (chemical compound classes, general use, ranges of concentra-tions/amounts used) that will not allow for identification of compound identities, products, pro-ducers or companies. Information received on any high risk additives will be kept in confidential files at DHI, whereas information received on all other additives will be returned to the company or destroyed as re-quired by the company. The current time schedule for the project envisages receipt at DHI of datasheets before Decem-ber 31st 2003, 1. review of data sheets and additional data requests prepared by DHI before
43 As additives are considered all compounds added to gasoline and diesel distillates at the refinery and at depots etc, that is both production, blending and performance additives, including oxygenates 44 Risks considered are the risks in case of spill and leakage to soil and groundwater
136
January 31st 2004, additional information received at DHI by February 29th 2004, and a draft re-port prepared by DHI by March 31st 2004. For the company: ______________________ __________ Name Date For DHI: ______________________ __________ Christian Grøn Date
137
138
A P P E N D I X F
Template for confidentiality agreement with the 5 additive producers
139
Confidentiality agreement This agreement is made in duplicate on June 25th 2004 between: Company, address hereafter called the company and: DHI Water & Environment, Agern Alle 5, DK-2970 Hørsholm, Denmark hereafter called DHI. The company and DHI has agreed on the following: The company will make data on chemical identities, concentrations and properties of additives available to DHI for all additives45 and additive products given in a separate survey of additive components and products used in Denmark. In addition, the company will give information on other additive components and products known to be added to gasoline and diesel distributed in Denmark by the company. The delivery of and use of data is described in the enclosed documents “assessment of addi-tives to fuels” and “screening for potential risk additives to gasoline and diesel”, both dated June 24th 2004, including a two step procedure for comments and additional data delivery for the company. DHI will keep all information confidential with access only by Christian Grøn, and the information will be stored separately under lock in the DHI alarm protected safe area used for storage of other strictly confidential information. DHI will review the data sheets and will if relevant request additional information on components not specified in the data sheets and further on toxicity, physical-chemical properties and persis-tence. The company will make the additional information available to DHI if available. DHI will review the environmental and human health risks potentially associated with the addi-tives and produce a list of potential risk46 additives and their properties, if any such additives are identified. The information on potential risk additives can be published in a report to the Danish client that will be made available to the public. Information on all other, non risk additives will only be published in generic terms (chemical compound classes, general use, ranges of con-centrations/amounts used) that will not allow for identification of compound identities, products, producers or companies. Information received on any potential risk additives will be kept in confidential files at DHI, whereas information received on all other additives will be returned to the company or de-stroyed as required by the company. The current time schedule for the project is described in the enclosed document “screening for potential risk additives to gasoline and diesel”. For the company:
45 As additives are considered all compounds added to gasoline and diesel distillates at the refinery and at depots etc, that is both production, blending and performance additives, including oxygenates 46 Risks considered are the risks in case of spill and leakage to soil and groundwater
140
______________________ __________ Name Date For DHI: ______________________ __________ Christian Grøn Date
141
142
A P P E N D I X G
Key properties used in the risk screening for additive com-pounds assigned a potential added risk
143
The properties behind the suggested added risks are given in the table. Compound S P Classifications for particular risk for human
health and/or the environment
Name CAS number g/L Pa Human health
Environmental hazard
2-Propanol 67-63-0 1000 - - -
Triethanolamine 102-71-6 1000 - - -
2-Ethylhexan-1-ol 104-76-7 0.88 18 - N: R51/53
Diethanolamine 111-42-2 1000 - - -
2-Buthoxyethanol 111-76-2 1000 - - -
1,2-bis(2-Ethylhexyloxycar-bonyl)ethanesulphonate potassium salt
7491-09-0 24 - - -
2-Ethylhexyl nitrate 27247-96-7 0.013 - - -
Tetrapropenylbutanedioic acid 27859-58-1 23 - - -
1,2-Ethanediamine reaction products with chlorinated polyisobutylene
68891-84-9 10 400 - -
Maleic acid tridecylamide 84583-68-6 39 - - -
1-Propene, 2-methyl-, homopolymer, hydrofomylation products,
337367-30-3 0.5 - - -
Polyalkylene polyamine nd47
1000 - - N: R51/53
Polyolefin Mannic base nd 40 - - -
47 No CAS no. given 144
145
