Fuel additives

145 Pages·2007·2.16 MB·English

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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