Service Bulletin

Measuring Residual Fuel Contamination

in Marine Diesel Engine Oils
Background of Measuring Heavy Fuel Dilution in Medium Speed Engine Oils
The contamination of medium-speed engine lubricants with residual fuel continues to be a common problem. Contamination can
occur through leaky fuel pumps or faulty fuel injectors or as the result of poor combustion. The effects of fuel contamination are
varied and usually detrimental to lube oil properties. Fuel contamination can affect the lube oil viscosity, dilute the additives and
increase the volatility of the lube oil, which may cause a safety and/or reliability problem in the engine barring other factors.
The ability to detect fuels in used engine lubricants depends greatly on how dissimilar the
fuel and the lubricant are to each other. Detection of gasoline in used engine oils may be
straight forward due to their significant differences in boiling range. Whereas, detection of
residual or bunker fuel in heavily additized marine engine oils is not so straight forward.
Both the lubricating oil and residual fuel are hydrocarbons with similar boiling ranges.
Furthermore, several physical properties such as viscosity and pour point are similar
enough and have enough variability that detecting and measuring fuel contamination is
difficult 1. Still, residual fuel typically has three distinguishing properties. Nearly all contain
asphaltenes as well as nickel and vanadium at various levels. Capitalizing on these
properties provides an excellent way to detect residual fuel in used engine oils.
In general, nickel and vanadium are benign contaminants. They are usually present in used
marine engine oils. Both can enter the oil by passing the piston rings as blowby or by direct
contamination through leaky fuel pumps, etc. In unburned residual fuel, these metals are
largely present in a porphyrin structure. Porphyrins are ring-like structures containing carbon,
hydrogen and nitrogen. The nitrogens in porphyrins can bind to many metals, including nickel
and vanadium as shown in Figure 1. Vanadium in residual fuel also is bound to one oxygen
atom (V=O), which is the vanadyl form. When the fuel is burned, nickel and vanadium form
nickel oxide (NiO) and vanadium pentoxide (V2O5). So the nickel and vanadium in used
marine engine oils can be a mixture of metal porphyrins and metal oxides.

Figure 1. Metallated
Etioporphyrin10 Where M is Ni or
V=O (Vanadyl), N is Nitrogen,
Carbon is on End of Each Line
Segment, and Hydrogen is not
Represented.

RFD Versus Detecting Asphaltenes Contamination (DAC) Methods

The ExxonMobil Residual Fuel Detection (RFD) Method 2 takes advantage of this chemistry and measures the vanadium still in
the porphyrin form. This vanadium was never oxidized to vanadium pentoxide as a result of combustion. It remains as a vanadyl
porphyrin. Therefore, the RFD test result is an indexed measure of unburned fuel contamination. The vanadium contaminant
itself is of little concern in the lube oil. 3 One limitation of the RFD Method is that vanadium levels in fuel oils can vary considerably.
This makes difficult the estimation of fuel dilution in absolute terms, but it does act as an indicator of residual fuel components in
the lube oil. Trending the results and having knowledge of the fuel-in-use help to quantify the severity of contamination. Still,
vanadium is not the best fuel property to measure and neither is nickel. The best fuel oil property to measure in lube oils is
asphaltenes, since these are the molecules detrimental to the engine.
Asphaltenes are naturally occurring in crude oil. They are a class of organic molecules that have high molecular weight and are
high boiling (>600F). As a result, they concentrate in the bottom distillation fractions at refineries along with other heavy
hydrocarbon molecules. These fractions are the major components in marine fuels. There is no specification for asphaltenes in
residual fuels, but levels typically do not exceed 13 wt. %. 4 Average levels are about 6-7 wt. %. Asphaltenes in fuel present two
significant problems. (1) They have poor combustion properties, and (2) they can be destabilized and drop out of the oil, resulting
in a tacky sludge. Both problems can affect the lubricant.

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As with nickel and vanadium discussed above, asphaltenes can get into engine lubricants through the same pathways.
Asphaltenes, however, are not benign contaminants. They can result in sludge formation. They can also cause the viscosity to
increase, and they degrade oxidation properties of the lubricant. In addition, the presence of residual fuel, particularly
asphaltenes, in the lube oil is known to promote piston undercrown deposits, which can lead to piston crown burning.5-9
Figures 2a and 2b show examples of clean and heavy piston deposits. Figure 3 provides an example when the undercrown
deposits become high enough to lead to piston crown burning. So, a measurement of asphaltenes in used lube oil would be a
direct measure of the worst offending residual fuel contaminant.
The acceptable level of asphaltenes in engine lubricants is not well established, but 1.0 wt. % is generally considered high
regardless of the fuel source or its asphaltenes content. Only rarely does the asphaltenes content reach 2.0 wt. %. Most modern
marine engine lubricants, including the Mobilgard M-Series, are formulated to control sludge formation from fuel contamination.
So, little sludge is formed in the engine now, and purifiers are unable to remove most asphaltenes from the lube oil because
additives help to stabilize them. Figure 4 illustrates the way partially burned fuel induced asphaltenes contamination occurs.
The picture shows that the asphaltenes enter from the combustion chamber and travel into the crankcase and its lubricating oil.
This contamination can result in deposits in the crankcase or deposits in the piston undercrown as the lubricating oil travels
through the piston stem to the piston undercrown. Figure 5 shows the difference between a high performance medium-speed
diesel engine oil, Mobilgard M Series, and a lower performance competitive lubricant's ability to handle fuel contamination.
The major effects of their presence are elevated lubricant viscosity and/or low lubricant Total Base Number (TBN).

Figure 2a. This picture illustrates a

clean piston undercrown.

Figure 2b. This picture illustrates a

piston undercrown with heavy deposits.

Figure 4. This schematic shows the basic path

for asphaltenes from partially burned fuel in the
combustion chamber to enter the engine oil, the
engine crank case, and up the piston stem to
the piston undercrown.

Figure 3. This picture illustrates a hole

burned into a piston crown caused by
piston undercrown deposits resulting in
poor heat transfer.

Figure 5. This picture illustrates the

difference between two different oils
detergency and capability to prevent
sludging.
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Finding a suitable method to measure asphaltenes in used marine engine lubricants has been difficult. Their typical concentration
is too small for most potential methods, such as n-pentane or n-heptane precipitation, to work with reasonable precision.
However; the Central European Coordinating Council (CEC) for the development of tests for lubricants and fuels is currently near
standardizing a method that measures asphaltenes in used marine engine oils with good accuracy. The method, CEC L-94, uses
Gel Permeation Chromatography (GPC), which is also known as Size Exclusion Chromatography (SEC). As the latter name
implies, the method sorts molecules by size, and they can be detected by various means. With this method, asphaltenes in
marine engine oils can be detected and quantified. A detailed description of this method has been published elsewhere.9
The advantage of the CEC test over the RFD test is that the most offending residual fuel component in used engine oils is
measured directly. The RFD test offers an indirect method of measuring asphaltenes, since vanadium levels often trend with
asphaltenes levels, but there are many exceptions. Vanadium in the oil does not adversely affect lube oil properties, so its direct
measure has little value other than verifying that unburned fuel components are present and that they roughly correlate with
asphaltenes and fuel. Measuring asphaltenes directly is preferred, since these molecules can affect engine and lubricant
performance.
CEC L-94, however, is difficult to automate for use in a commercial, high volume used oil analysis lab. Therefore, ExxonMobil
Research and Engineering (EMRE) has developed a proprietary automatable method that correlates well with CEC L-94
asphaltenes results. This new EMRE test is termed, Detecting Asphaltenes Contamination (DAC). DAC reports asphaltenes in
wt. %. Note that DAC is formulation specific, so the analysis of competitive lube oil samples may not be possible.

Determining the Amount of Heavy Fuel Dilution in the Lubricating Oil

How much fuel is in the lube oil? This is a persistent question that is very difficult to answer and often makes little sense to
calculate. As with the RFD test, it is possible to calculate a per cent fuel contamination, if a history of fuel-in-use is known in
terms of vanadium content. Similarly, per cent fuel contamination can be calculated if a recent history of the fuel asphaltenes
levels is known. Making this calculation, however, assumes that raw (unburned) fuel contaminates the lube oil. This is less often
the case now in modern medium-speed engines. Much of the contamination comes from fuel entering the combustion chamber
and being partially burned. Some asphaltenes survive and blow past the piston rings like soot, but the light end (lower boiling
components) of the fuel burns off. So, calculating per cent fuel contamination in this case is a debatable point. Most of the fuel
never enters the lube oil, only the very heavy end (higher boiling components including asphaltenes).

Determining Raw versus Partially Burned Fuel Dilution

It should be noted that CEC L-94 is capable of distinguishing unburned fuel contamination from partially burned fuel contamination
in the lube oil.9 The EMRE DAC method that correlates with the CEC L-94 measures asphaltenes but cannot distinguish the two
types of contamination. However, the lube oil viscosity generally increases faster with partially burned fuel contamination, reflecting
the loss of the lower boiling fuel components through combustion. So, the use of viscosity as a secondary indicator can help to
distinguish the types. If desired, the types can be confirmed by running the CEC L-94.
Thus, the measurement of asphaltenes in used marine lubricants offers a significant refinement of the current RFD test. Both
methods have the same objective, i.e. measurement of residual fuel components, but the direct measure of asphaltenes is better
aimed at the most offending residual fuel component. The new CEC L-94 standard test offers good information on asphaltenes
levels and on whether they were derived from partially burned or unburned fuel. The new EMRE method measures the
asphaltenes content only, but this is about 90% of the value of CEC L-94, and secondary indicators should provide most of the
remaining value. Furthermore, the EMRE method is easily implemented into a high production used oil analysis laboratory such
as the Signum Lab.

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Guidance for Interpreting Signum DAC Results

Due to the complex nature of asphaltenes contamination in lubricating oils, ExxonMobils Signum program assigns an overall
rating of Caution if the DAC level exceeds 1.0 % for a sample. Again due to the complexity of asphaltenes contamination,
Signum supplies some general guidance that includes the suggestion that customers consult with ExxonMobil representatives to
discuss the appropriate course of action.
General guidance when high DAC levels (over 1%) are detected:
1. Consult with XOM Engineering and OEM for guidance.
2. If the DAC asphaltenes level is ~ 1.0% and the viscosity is high (defined by either Caution or Alert levels). The type of
fuel contamination is most likely partially burned. Consult to determine proper engine combustion characteristics, fuel
quality, etc. If continued high DAC levels exist then consider increasing frequency of piston undercrown, crankcase, etc.
inspections.
3. If the DAC asphaltenes level is > 1.5% and the viscosity remains satisfactory (defined by the absence of Caution of Alert
levels). The type of fuel contamination is most likely unburned. Check for likely contamination sources such as leaking
injectors, fuel pumps, etc.
4. Mixtures of partially burned and unburned fuel contamination are possible.
5. High DAC asphaltenes may require lubricant charge replacement or sweetening.

References
1. Fabriek, W. P., Montaud, A., Vrolijk, D. J. E., Lim, K. C. & Dunn, A., Effects and Determination of Raw Fuel Dilution in
Marine Crankcase Lubricants, CIMAC Proceedings, Copenhagen 1998, pp. 951-965.
2. Reischman, P. T., The Residual Fuel Detection (RFD) Test A Vital Component to Used Engine Oil Analysis and Engine
Condition Monitoring, CIMAC Proceedings, Copenhagen 1998, pp. 1747-1754.
3. Vanadium in the fuel is a potential problem for hot corrosion, if the V/Na ratio is near 3. Vanadium in the lube oil is of no real
concern, except for what it indicates.
4. As measured by precipitation with n-heptane, such as IP 143, DIN 51595, ASTM D3279, ASTM D6560, Mobil Method 1302
or analogous method.
5. Guidelines for Diesel Engines Lubrication Impact of Fuel on Lubrication, CIMAC Document No. 18 / 2000.
6. Verlinde, M. & Boons, M., TPEO Formulating Challenges for Increased Oil Change Intervals, CIMAC Proceedings, Paper
No. 115, Kyoto 2004,
7. Jakobsen, S. B. & Jensen, H. R., Service Experience with the S90MC-C / ME-C, Cylinder Condition, MAN B&W Diesel
Document 2300/HRJ/MER/6932-2006, 28 February 2006.
8. Meeting the Lubrication Challenge, The Motor Ship, July/August 2004, p. 6.
9. Gehring.H. & van Geeteruyen, C., Diesel and Gas Turbine World Wide, June 2006, pp. 40-44.
10. Branthaver, J. F., Influence of Metal Complexes in Fossil Fuels on Industrial Operations, Metal Complexes in Fossil Fuels,
ACS Symposium Series 344, ed. Filby & Branthaver, 1987, pp. 188-204, American Chemical Society, Washington, D.C.

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