United States
Environmental Protection
Agency
Motor Vehicle Emission Lab
2565 Plymouth Rd
Ann Arbor, Michigan 48105
EPA-460/3-81-008
March 1980
Air
Nitrosamine Analysis of
Diesel Crankcase Emissions
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EPA-460/3-81-008
NITROSAMINE ANALYSIS OF DIESEL
CRANKCASE EMISSIONS
David H. Fine
Ulku Goff
New England Institute for
Life Sciences
125 Second Avenue
Waltham, Mass. 02154
Contract No. 68-03-2719
EPA Project Officer: Thomas M. Baines
Prepared for:
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF AIR, NOISE AND RADIATION
OFFICE OF MOBILE SOURCE AIR POLLUTION CONTROL
EMISSION CONTROL TECHONOLOGY DIVISION
ANN ARBOR, MICHIGAN 48105
March 1980
,
U.S. Environ-""- >3
Caicago,
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This report is issued by the Environmental Protection Agency to disseminate technical
data of interest to a limited number of readers. Copies are available free of charge to
Federal employees, current contractors and grantees, and nonprofit organizations—in
limited quantities—from the Library, Motor Vehicle Emission Laboratory, Ann Arbor,
Michigan 48105, or, for a fee, from the National Technical Information Service, 5285
Port Royal Road, Springfield, Virginia 22161.
This report was furnished to the Environmental Protection Agency by New England Institute
for Life Sciences, 125 Second Avenue, Waltham, Mass. 02154, in fulfillment of Contract
No. 68-03-2719 The contents of this report are reproduced herein as received from New
England Institute for Life Sciences. The opinions, findings, and conclusions expressed are
those of the author and not necessarily those of the Environmental Protection Agency.
Mention of company or product names is not to be considered as an endorsement by the
Environmental Protection Agency.
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Report No. TE450-259-81
Final Report
NITROSAMINE ANALYSIS OF DIESEL
CRANKCASE EMISSIONS
Contract No. 68-03-2719
Prepared by:
David H. Fine and Ulku Coff
New England Institute for Life Sciences
125 Second Avenue
Waltham, MA 02154
Prepared for:
The Environmental Protection Agency
2565 Plymouth Road
Ann Arbor, Ml 48105
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TABLE OF CONTENTS
Section Paae
FOREWORD v
I. INTRODUCTION 1-1
II. SUMMARY II-l
III. EXPERIMENTAL III-l
A. Materials III-l
B. Apparatus III-2
C. Procedures III-3
IV. DISCUSSION OF RESULTS IV-1
APPENDIXES
A. Scope of Work A-l
B. Diesel Fuel Analysis for Nitrosamines B-l
C. Engine Variable Measurements C-l
D. Comparison of GC-TEA and GC-MS Result D-l
E. The Information Supplied by Various Engine
Manufacturing and Oil Companies E-l
F. The Results of the Used Oil Samples Acquired by
The New England Institute for Life Sciences F-l
G. Nitrosamine Measurements Taken During Method
Development Period G-l
H. Diesel Tailpipe Exhaust Analysis for Nitrosamines H-l
I. Nitrogen Content of Some of the Oils 1-1
J. Background on Nitrosamines j-1
REFERENCES K-l
iii
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FOREWORD
This report covers EPA contract no. 68-03-2719 conducted for the
Environmental Protection Agency, 2565 Plymouth Road, Ann Arbor, MI 48105. The
EPA project officer was Mr. Thomas M. Baines. The principal investigator for
New England Institute for Life Sciences was Dr. David H. Fine and Laboratory
Manager was Ms. Ulku Goff who was assisted by Mr. James Coombs. The project was
performed during the period of September 11, 1978 through December 12, 1979.
v
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1-1
I. INTRODUCTION
Amine type compounds are often present in lubricating oil as friction
modifiers, metal deactivators, dispersants and corrosion and rust inhibitors
(Schilling, G.J., Bright, G.S. 1977). Oxides of nitrogen (NOX) are generated
in situ during the combustion process in the combustion chamber. Because
N-nitrosation of amines via oxides of nitrogen has been shown to be rapid,
especially in nonaqueous solvents (Challis, B.C. et al., 1978), nitrosamines
are to be considered likely contaminants in diesel crankcase emissions.
Challis et al. , (1978) reported rapid formation of N-nitrosamines by
gaseous oxides of nitrogen (^O-j, ^0^) in organic solvents. Both
N203 and N204 are used as nitrosating agents for the synthesis of
N-nitrosamide in organic solvents (White, E.H., 1955). Formation of
N-nitrosamines in cigarette smoke from dinitrogentrioxide (l^C^) has been
demonstrated by Neurath et al., (1976) and Spincer and Westcott (1976).
Keefer et al., (1976) observed that relatively small amounts of metal
salts catalyze the nitrosation action of nitric oxide (NO) in organic solvents.
Challis et al., (1978) have observed the catalytic effects of metal salts such
as ZnI2, ZnBr2, CuCl2, Fe(N03)3, AgN03 and CuSo^ for NO nitrosa-
tion reaction. They also found that the metal salt catalyzed reactions in
organic solvents were substantially faster than N-nitrosamine formation by
acidified nitrite (Challis, B.C., and Outram, J.R. 1978).
Zinc dithiophosphate is added into automotive lubricating oils, (Schilling,
G.J. and Bright, G.S. 1977) to reduce friction between metal parts, decrease
wear and prevent corrosion and rusting of metal parts that are in contact with
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II-l
the lubricant. The salt also retards the oxidative decomposition of the oil
(Schilling, G.J. and Bright, G.S., 1977). A catalytic effect of this salt
mij'.lit be expected during NO nitrosation of amines in the oils.
Although NDMA has not been observed to be present in automobile exhaust, it
has been detected in Colorado's Eisenhower road tunnel (Hare, C.T. Montalvo,
D.A., ]977a). Gordon's work has indicated the presence of highest levels of
NDMA on the grounds of the Los Angeles County-University of Southern Califor-
nia Medical Center which is located near the Golden State Interchange and San
Bernadina Freeways and is also close to the local traffic (Gordon, R.J, 1978).
This has suggested a relationship with the vehicle emissions and the NDMA
levels. Cadle, S.H. and Mulawa, P.A. concluded that the exhaust emissions
of amines from current-production automobiles cannot account for nitrosamine
levels measured in the Eisenhower Tunnel in Colorado and on Cross-Bronx
Expressway in New York City (Cadle, S.H., Mulawa, PA, 1980). Previous research
on diesel engine crankcase emissions as a source of nitrosamine emissions has
been inconclusive. In a recent study, NDMA was detected using a gas chromato-
graph (GC) interfaced to a nitrogen selective Hall detector; confirmation of
the finding by GC-mass spectrometry (MS) was complicated by co-eluting compounds
(Hare, C.T., Montalvo, D.A., 1977b). An analysis of diesel crankcase emissions
contained in Tedlar bags did not indicate that NDMA was present (Hare, C.T.,
Montalvo, D.A., 1977c.). When positive results were obtained, little effort was
addressed to the possibility that the nitrosamines were being formed as analy-
tical artifacts, either during trapping, or during analysis. A background on
nitrosamines is given in appendix J.
11. SUMMARY
The main objective of this work was to qualify and employ artifact-free
methods in the testing of crankcase emissions of heavy-duty diesel engines for
volatile N-nitrosamines (See Appendix A for the scope of work). In order to
achieve this objective the following tasks were performed.
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II-2
TASK I. Sampling and Analysis Method Development and Qualification
This objective was achieved by developing a crankcase sampling method that
involved trapping the volatile nitrosamines in either a pH 4 phosphate-citrate
buffer solution or in a Thermosorb™/N Air Sampler, followed by extraction of the
traps with appropriate solvents, concentration and analysis of the material on a
gas chromatograph and/or high pressure liquid chromatograph interfaced to a
TEA™ Analyzer.
Detection limits, based on a 60L sample, were 0.1 yg/m^ for N-nitroso-
dimethylamine (NDMA) and 0.16 yg/m^ for N-nitrosomorpholine NMOR. Validation
of the reliability of the method included the intentional addition of both
amines and/or nitrogen oxides. Confirmation of the identify of the nitrosamines
was accomplished by high resolution mass spectrometry.
TASK II. Engine Selection
Test engine selection was made so that the influence of the engine type
could be determined. For this reason a total of four engines, 3 heavy-duty (HD)
and one light-duty (LD) were selected.
TASK III. Engine Testing
This objective was achieved by obtaining crankcase emission samples from
the HD test engines during a 7-mode schedule and from the LD test engine during
a 2-mode schedule and analyzing these samples for volatile nitrosamines by the
methods described in TASK I. One of the engines selected was tested with four
different types of lubrication oils to establish the influence of the oil type.
The 7 modes used for heavy duty testing were modes 2, 4, 6, 7, 8, 10, 12 of the
Federal 13 mode sequence. The light duty testing was performed at 20 and 50
mph.
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II-3
All the'samples obtained during engine testing contained NDMA at levels
ranging from 0.2 uK/m^ to 28 yg/m^ and some samples contained NMOR at levels
between 0.2 pg/m^ and 2 ug/m .
As we worked toward the achievement of the main objective of this work, we
also attempted to establish the sources of the crankcase emission nitrosamines.
We examined the lubricating oils and the diesel fuels (see Appendix B). As we
gathered more information, new objectives were set.
As a second objective, a survey of nitrosamine levels in unused, and used
oils was set, for which the following tasks were carried out.
TASK IV. Oil Analysis Method Development
This task was performed by developing an oil analysis method that involved
the transfer of volatile nitrosamines by bubbling air through the heated oil
sample onto a ThermoSorb'"/N Air Sampler, followed by elution of the sampler
with acetone and analysis of the eluate on a gas chromatograph interfaced to a
TEA. Detection Limits, based on 50 gm sample, varied from 0.1 part-per-billion
(ppb) for NDMA to 1.0 ppb for N-nitrosodibutylamine (NDBA). Artifact
experiments were carried out by intentional addition of amines into the oil
samples and the TherraoSorbIH/N Air Sampler for the validation of the method.
TASK V. Selection and the Survey of Oil Samples
This task was achieved by conducting:
a) A survey of the nitrosamine levels in unused oil samples to determine
the effect of the oil type.
b) A survey of the used oil samples that had been obtained at progres-
sive time intervals of usage, to determine the effect of the usage
duration on the nitrosamine levels.
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III-l
As a third objective, a relationship between the nitrosability of the oils
and the engine crankcase nitrosamine levels was sought so that nitrosamine
levels could be predicted based on nitrosamine formations from the unused oils
in tests conducted in the laboratory.
To complete this objective the following tasks were conducted.
TASK VI. Oil Nitrosation Method Development
This objective was achieved by developing a method of nitrosation of the
nitrosamine precursors in the oils which involved bubbling a NO/NC>2 gas
mixture through the sample. The nitrosamines formed were picked up by the gas
stream and collected on a ThermoSorb'"/N Air Sampler which was then eluted with
acetone and the eluate analyzed on a gas chromatograph interfaced to a TEA™.
TASK VII. Survey of the Nitrosability of the Oils
This test was performed by nitrosating unused and used oils samples that
were acquired from oil and engine manufacturing companies. The nitrosated
unused oils contained NDMA at levels from nondetectable to about 200 ppb and
NMOR at levels between nondetectable and about 25 ppb.
III. EXPERIMENTAL
A. MATERIALS
Organic solvents (Distilled in Glass™) were obtained from Burdick and
Jackson (Muskegon, Ml). Morpholine (Reagent ACS), piperidine (practical),
pyrrolidine (practical), dipropylamine (practical) were obtained from Eastman
Kodak Company (Rochester, NY). Dimethylamine (40%), and L-Ascrobic Acid were
obtained from Aldrich Chemical Company (Milwaukee, Wl). Standard nitrosamine
solutions and ThermoSorb'"/N Air Samplers were obtained from the Analytical
Services Laboratory of Thermo Electron (Waltham, MA).
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III-2
The pH 4 phosphate-citrate buffer, sulfamic acid (certified), and sodium sulfate
(anhydrous certified ACS) were obtained from Fisher Scientific Corp. (Fairlawn,
NJ). Gas mixtures of NO + N02 prepared in nitrogen (^) were obtained from
Scientific Gas Products (South Plainfield, NJ). DL-tocopherol was obtained from
Chemalog (Chemical Dynamics Corp., South Plainfield, NJ). The GC packing
material, 10% Carbowax 20M, 0.5% KOH on Chromosorb WHP 80/100, was obtained from
Analabs, Inc. (North Haven, CT). The used and fresh oil samples were obtained
from various U.S. oil and engine manufacturers.
B. APPARATUS
The gas chromatography (GC) analyses were carried out with a Thermo
Electron GC-661 interfaced to a TEA™ (Thermo Electron Corp., Waltham, MA). The
GC column was packed with 10% Carbowax 20M and 0.5% KOH on Chromosorb WHP,
80/100 in a 1/8" o.d. x 12" long stainless steel tube. NDMA analyses were
carried out at 110°C; the other volatile nitrosamines were analyzed at 175°C.
The high pressure liquid chromatograph (HPLC) analyses were carried out with a
Varian 8500 LC pump (Varian Instrument Division, Palo Alto, CA) interfaced to a
TEA™. The liquid chromatogrphy (LC) column was a porasil 10 (3.9 mm x 300 mm)
(Waters Associates, Milford, MA), used with a solvent system that contained 4
to 8% acetone in isooctane. The LC injector was a model U6K (Waters
Associates). Bendix Mesa C-116 air pumps (Bendix Corporation, Rochester, NY)
were used for sample collection.
Air flow rates of the pumps were calibrated against a Hastings ALL 10 L
mass flow meter (Teledyne Hastings-Raydist, Hampton, VA). The method
development and validation for crankcase emission analyses were carried out
using a Mack ENDT 676 engine located at Thermo Electron Corporation.
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III-3
The nitrosamine measurements of crankcase emissions were made on Mack ETAY (B)
673A, Detroit Diesel 6V-71N, Caterpillar 3406, and a Mercedes Benz 240D which
were operated by the Emissions Research Department of Southwest Research
Institute (SWRl), San Antonio, TX.
C. PROCEDURES
TASK I. Sampling and Analysis Method Development and Qualification
Two trapping techniques were developed: dry traps consisting of a
ThermoSorb'"/N Air Sampler in series with a sulfamic acid cartridge, and a liquid
trap consisting of a phosphate-citrate buffer at pH 4 in a glass impinger tube.
Crankcase emissions from the engine were collected by means of a toggle valve
(i.d. 1/4") or manual rotary valve (i.d. 1/4") situated on the breather pipe
housing of the engine cover. Parallel sampling was done after splitting the
teflon line a few inches from the valve by means of a elastic tubing connector
(Pharmaseal Inc., Toa Alto, P.R.). The connector and the traps were connected
by 1 to 2' of teflon tubing (o.d. 1/4", i.d. 1/8"). The sample collection
apparatus is illustrated in Figure 1. Each HD engine was run through seven
different 1/2 hour test modes during which engine speed and load were kept
constant. Separate samples were collected during each mode at a flow rate of
21,/min.
(Descriptions of the heavy- and light-duty engines and the measurements of
the engine speed, load, power, water and crankcase temperatures, crankcase NO
and N02 concentration and flow rates in each test mode were provided by SWRI
and are given in Appendix C.) Precise time and flow data were used to calculate
sample throughput. After collection, the samples were stored in a dry ice box
or freezer until the time of analysis.
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Engine Crankcase
pH: 4 Buffer Traps
Sulfamic
Acid
Cartridge
ThermoSorb™ / N
Air Sampler
Sampling Pump
Sampling Pump
Sampling Time: 1/2to1hr
Flow Rate: 2L/min
Figure: 1 Sample Collection from Crankcase Emissions
M
I
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III-5
1. ThermoSorbw/N Air Sampler/Sulfaraic Acid Cartridge
According to the supplier, TherraoSorb™/N Air Samplers were developed for
artifact-free collection of N-nitrosamines from ambient air (Rounbehler, D.P. et
a 1. , 1980); for sampling air from diesel engine crankcase emissions, the
relatively high nitrogen oxide (NOX) levels necessitated placing a sulfamic
acid cartridge in front of the ThermoSorbI"/N Air Sampler. Sulfamic acid reacts
with the incoming NOX and amines, thus preventing possible artifactual
nitrosation on the ThermoSorb™/N Air Sampler at high NOX levels (Goff, U.G.
and Coombs, J.R. , 1979, unpublished work).
At the end of the sampling period the ThermoSorbIH/N Air Sampler and sulfamic
acid cartridges were removed and separated. The ThermoSorb'"/N Air Sampler was
washed to remove nonpolar oily materials by reverse eluting (See Figure 2) with
10 ml pentane followed by 2 ml of a mixture of dichloromethane and pentane
(5/95). The cartridge was then dried by blowing carrier gas through it. The
N-nitrosamines were finally eluted from the cartridge with 1.5 to 2.0 ml
acetone. A 10 to 25 yl aliquot of the acetone fraction was introduced into the
GC-TEA or HPLC-TEA.
?. Phosphate-Citrate pH 4 Buffer Traps
These traps consisted of two glass impingers (240 x 30 mm) in series, each
containing 40 ml of a phosphate-citrate solution buffered at pH 4 together with
0.5 to 1 g sulfamic acid. The traps were immersed in an ice bath. The sulfamic
acid was used because it inhibits nitrosation (Fan, T.Y. et al., 1977a) by
competing with amines for the nitrosation agent. At the end of the sampling
time the trap contents were transferred into separatory funnels and extracted
with 2 x 10 ml pentane to remove the nonpolar oily materials from the aqueous
phase. The pentane fraction was discarded. The trap contents were then extrac-
<"i with 3 x 10 ml of dichloromethane (DCM), which extracted the nitrosamines.
The DCM fraction was dried by passing the sample through a funnel containing 25
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Sulfamic
Acid ThermoSorb™/N
Cartridge Air Sampler
\
f \ \ ft \
Sample ^ -* *- -1 u-
A B
1. 10ml Pentane wash from B to A.
2. 2 ml 5/95 Dichloromethane/Pentane wash from B to A.
3. Dry the cartridge by blowing carrier gas through it.
4, 1.5-2 ml Acetone wash from A to B.
rpv*
Figure: 2 Extraction of Nitrosamines from ThermoSorb /N
Air Sampler
H
H
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III-7
sodium sulfate and then was concentrated in a Kuderna Danish evaporator to 1 ml.
A 10 to 25 yl aliquot of the DCM concentrate was introduced into GC-TEA and/or
HPLC-TEA for analysis.
ARTIFACT CONTROL EXPERIMENTS
A series of experiments were carried out to ensure that if nitrosamines
were detected they were present in the engine crankcase emissions at the
calculated amounts, and were not being formed during sampling and/or analysis.
1. Tests with Phosphate-Citrate Aqueous Traps
Recovery studies were carried out by adding 500 ng each of NDMA,
N-nitrosodiethylamine (NDEA), N-nitrosodipropylamine (NDPA), N-nitrosodibutyl-
amine (NDBA), N-nitrosopiperidine (NPiP), N-nitrosopyrrolidine (NPYR) and
N-nitrosomorpholine (NMOR) vto the traps and passing 200 L of air through the
traps at a flow rate of 2 L/min. The recovery efficiency for NDPA and NDBA was
inadequate (see Table 1), and the liquid traps cannot be used for these two
nitrosamines. For the two nitrosamines of interest, NDMA and NMOR, however, the
recovery was 77 and 82%, respectively.
The overall efficiency of the aqueous buffered traps were tested by
introducing 500 ng each of the mix of 7 nitrosamines into the incoming air
stream prior to two traps in series. In all cases, 96% of the recovered
nitrosamines were found in the first trap.
The possibility that nitrosamines could be formed artifactually during
collection and/or analysis was tested both in the laboratory and during tests on
a diesel engine. Dimethylamine (DMA), piperidine (PIP), pyrrolidine (PYR) and
morpholine (MOR) were used as the test amines. DMA and MOR were selected
because the nitrosamine derivatives of DMA and MOR were found to be present in
crankcase emissions; piperidine and pyrrolidine were selected with the thought
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III-8
that they would make the artifact formation of nitrosamines more recognizable
since NPiP and NPYR don't exist in the emissions.
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III-9
Table 1
Extraction Efficiency of Various Nitrosamines
(500 ng each) from pH 4 Phosphate-Citrate Buffer Traps (40 ml)
Nitrosamin.e ^ Recovery (%)*
NDMA
NDEA
NDPA**
NDBA**
N-PiP
NPYR
NMOR
77
66
9
N.D.
66
88
82
* The recovery is the average of two measurements.
** These nitrosamines were extracted into the pentane layer.
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111-10
The laboratory simulation studies were carried out using the apparatus
shown in Figure 3. Fifty yg of each amine was added to the traps and the NO and
N(>2 concentration adjusted to 100 ppm and 7 ppm, respectively, by bleeding air
into the lines. This concentration of NOX is an approximation of the NOX
levels present in the crankcase emissions of the Mack 676 ENDT engine under
actual operating conditions. Two measurements were performed; one with 1/2 hr
sampling time, and the other with 1 hr sampling time. In each case the flow
rate was 2.0 L/min, (6 mg NO + 0.4 rag N02 for 1/2 hr sampling; 12 mg NO + 0.8
rag NC>2 for 1 hr sampling). In every case, the nitrosamine derivative of the
added amines could not be detected (sensitivity level per trap 0.006 yg NDMA,
0.018 yg/ NPiP, NPYR and NMOR).
The artifact studies during engine operation were carried out using the
Mack 676 ENDT engine, using typical operating conditions. At the time, the NDMA
level in the crankcase blowby was 0.1 yg/m^. Four experiments were conducted
(see Table 2). In the first, 50 yg of MOR was added to the trap - NMOR was not
found in the trap. Second, 50 yg of PYR was added to the trap - NPYR was not
found in the trap. Third, using identical parallel traps, 50 yg, of DMA was
added to one of the traps - no enhancement of the NDMA level was found when
compared to the control trap. Fourth, using identical parallel traps, 63 yg of
PYR was added to both traps. One of the parallel traps received an additional
14 mg of NO + 1 mg N02 (100 ppm NO and 7 ppm N02 in the gas stream).
Neither of the two traps contained enhanced levels of NDMA, or detectable levels
of NPYR.
The Teflon tubing connecting the crankcase to the traps was checked for the
artifactual formation of nitrosamines. During engine sampling two liquid traps
(contin. on p. 111-31)
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NOX Source
\
1000 ppm NO
70 ppm N(>2 in N2
Air Bleed
Air Bleed
100 ppm NO
7 ppm HO2 in N2 and Air
pH:4 Buffer Traps
pH: 4 Buffer Traps
. Sampling Pump
2L/min
Sampling Pump
2L/min
Figure: 3 Simulated Engine Run With PH: 4 Citrate Phosphate Buffer Traps
M
M
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I
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111-12
Table 2
Results of Artifact Experiments with Amine Added to pH 4 Citrate-Phosphate
Buffer Traps During Engine Sampling
Flow Rate
Added Amine (L/min)
1. 50 yg/ morpholine 2.4
2. 50 yg pyrrol idine 2
3. 50 yg dimethylamine 2.1
None 2.1
4. 63 yg pyrrolidine 2.2
63 yg pyrrolidine* 2.2
NO + N02
Time Detection Lieht
(hr) Results (jig/trap]
.5 No nitrosomorpholine
formed
1 No nitrosopyrrolidine
formed
.5 0.1 yg/m3 NDMA
.5 0.1 yg/m3 NDMA
.5 No nitrosopyrrolidine
formed
.5 No nitrosopyrrolidine
formed
0.018
0.018
0.006
0.006
0.018
0.018
*NO + NOo were bled into this sample (see text).
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Table 3
Mack ETAY (B) 673A: Shell Rotella T SAE30
Nitrosaraine and NO.NOo Measurements
Test
Mode
1
1
2
2
3
3
4
4
5
5
6
6
7
7
Average
NDMA NDMA
(Mg/ni3) (yg/m3)
0.24
0.24 0.24
0.49
0.62 0.55
0.37
0.38 0.37
0.42
0.42 0.42
0.66(0.57)*
0.61 0.63
0.52
1.30 0.91
0.51
0.49(0.49)* 0.50
Average Average
NDMA NMOR NMOR
(ug/0.5hr) (yg/m3) (yg/m3)
0.5. N.D.
2.0 N.D.
2.2 N.D.
0.6 N.D.
5.3. N.D.
4.4 N.D.
1.2 N.D.
Average
NMOR NDMA(yg/0.5hr)
(yg/0.5hr) NO. NO x 1012 NO.N02
68 0.007
5200 0.0004
8500 0.0002
68 0.009
14000 0.0004
3400 0.001
200 0.006
N.D. - Not Detected
* - HPLC-TEA confirmation
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Table 4
Mack ETAY (B) 673A: Amoco 300 SAE 30
Nitrosamine and NO.N02 Measurements
Test
Mode
1
1
2
2
3
3
4
4
5
5
6
6
7
7
N.D. -
* _
Average Average
NDMA NDMA NDMA
(yg/m ) (yg/m ) (yg/0.5hr)
4.9(5.3)*
5.1 5.0 10.5
3.6
4.9 4.2 15.1
3.8
3.8 3.8 22.8
2.0
1.7 1.8 2.7
5.7(5.2)*
6.0 5.8 48.7
3.6
4.1 3.8 18.2
2.7
2.4 2.5 6.0
Not Detected
HPLC-TEA confirmation
Average Average
NMOR NMOR NMOR NDMA( yg/0 . 5hr ) „
(yg/m3) (yg/m3) (yg/0.5hr) NO.NO^x 101 NO.N02
N.D.
N.D. N.D. N.D. 100 0.1
N.D.
N.D. N.D. N.D. 7100 0.002
0.4
0.3 0.35 2.1 12000 0.002
N.D.
N.D. N.D. N.D. 26 0.1
N.D.
N.D. N.D. N.D. 11000 0.004
N.D.
N.D. N.D. N.D. 5100 0.003
0.6
0.4. 0.50 1.2 230 0.03
H
H
HH
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Table 5
Mack ETAY (B) 673A: Mobil Delvac 1200 SAE 30
Nitrosaraine and NO.N02 Measurements
Test
Mode
1
1
2
2
3
3
4
4
5
5
6
6
7
7
Average Average
NDMA NDMA NDMA
(yg/m3) (ug/in3) (pg/0.5hr)
20.6(18.4)*
21.1 20.8 43.7
15.2
15.3 15.2 54.7
12.2
12.8 12.5 75.0
9.5
7.4 8.4 12.6
11.4
11.6 11.5 96.6
8.0
6.9 7.4 35.5
5.5
6.8(6.7)* 6.1 14.6
Average Average
NMOR NMOR NMOR
(yg/m3) (yg/m3) (yg/0.5hr)
0.9
1.0 0.9 2.0
1.4
N.D. 0.7 2.5
1.7
1.4 1.5 9.3
0.8
0.8 0.8 1.2
2.0
2.3 2.1 18.1
1.6
0.8 1.2 5.8
1.0
0.9 0.9 2.3
NDMA(ug/0.5hr)
NO.N02x 10 12 NO.N02
220 0.2
7400 0.007
7400 0.01
76 0.2
12000 0.008
4600 0.008
180 0.08
N.D. - Not Detected
* - HPLC-TEA confirmation
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Table 6
Mack ETAY (B) 673A: Mobil Delvac Super 15 W 40
Nitrosamine and NO.NC>2 Measurements
Test
Mode
1
1
2
2
3
3
4
4
5
5
6
6
7
7
Average
NDMA NDMA
(yg/m3) (yg/m 3)
30.7
25.3(26.8)* 28.0
24.9
28.3 26.6
21.8
19.7 20.7
12.9
12.3 12.6
16.9
15.2 16.0
10.6
11.1 10.8
7.6
7.9(6.0)* 7.7
Average
NDMA
(yg/0.5hr)
58.8
95.8
124.2
18.9
134.4
51.8
18.5
Average
NMOR NMOR
(yg/m3) (yg/m3)
0.9
0.8 0.8
1.6
1.5 1.5
1.7
2.2 1.9
1.2
0.8 1.0
1.8
1.9 1.8
1.4
1.9 1.6
0.8
0.9 0.8
Average
NMOR
(pg/0.5hr) NO.NOgX 10 12
1.8 77
5.6 5400
11.7 13000
1.5 97
15.5 15000
7.9 4200
2.0 270
NDMA(yg/0.5hr)
NO . N02
0.8
0.02
0.009
0.2
0.009
0.01
0.07
* - HPLC-TEA confirmation
H
H
-------
Table 7
Detroit Diesel 6V71N; Mobil Delvac Super 15 W 40
Nitrosamine and NO.NC>2 Measurements
Test
Mode
1
1
2
2
3
3
4
4
5
5
6
6
7
7
Average Average Average
NDMA NDMA NDMA NMOR NMOR
(l-ig/m3) (yg/nr) (jjg/O.Shr) ( yg/m3 ) ( pg/m3 )
2.5
3.1 2.8 1.7 N.D.
3.9
4.2 4.0 2.4 N.D.
5.2
5.6 5.4 3.2 N.D.
3.8
3.2 3.5 1.0 N.D.
6.0(6.0)*
5.6 5.8 26.1 N.D.
3.2
3.6 3.4 6.1 N.D.
1.4
1.5(1.7)* 1.4 2.1 N.D.
Average
NMOR NDMA(ug/0.5hr)
(ug/0.5hr) NO.N02x 10 NO.N02
3.1 0.5
1.7 1.4
11.4 0.3
3.6 0.3
19.3 1.3
4.9 1.2
1.2 1.7
10
N.D. - Not Detected
* - HPLC-TEA confirmation
-------
Table 8
Caterpillar 3406; N; Mobil Delvac 15 W 40
Nitrosamine and NO.NC>2 Measurements
Average Average Average Average
Test
Mode
1
1
2
2
3
3
4
4
5
5
6
6
7
7
N.D. -
* _
*@ -
NDMA
(yg/m )
4.9(4.9)*
4.8
5.3
5.6
5.8
6.1
1.6
1.8
6.7(6.4)*
6.1
4.9
4.5
1.8
2.0
NDMA
(yg/m )
4.8
5.4
5.9
1.7
6.4
4.7
1.9
NDMA
(yg/0.5hr)
12.0
19.4
34.2
4.6
35.6
21.1
6.8
NMOR
(yg/m )
N.D.
N.D.
0.4
N.D.
N.D.
0.9
N.D.
N.D.
0.7
0.8
0.4
N.D.
N.D.
N.D.
NMOR
( yg/m )
N.D.
0.2
0.4
N.D.
0.7
0.2
N.D.
NMOR
(yg/0.5hr)
N.D.
0.7
2.6
N.D.
4.0
0.9
N.D.
NDMA(yg/0.5hr)
NO.N02x 10 NO.N02
2.7 4.4
51.4 0.4
88.6 0.4
1.7 2.7
510.6 0.07
116.8 0.2
0*@ *@
Not Detected
HPLC-TEA confirmation
Whereas there
Of the two and
was 37 ppm N02, there was
an unquantif iable ratio
zero NO,
of NDMA to
leading to
NO.N02
a zero product
i — i
M
M
H-1
oo
-------
Table 9
Mercedes-Benz: Mobil Delvac Super 15 W 40
Nitrosamine and NO.N02 Measurements
Vehicle
Speed
(raph)
20
20
50
50
NDMA
(yg/m3)
2.9
3.3(3.7)*
4.6
4.6(5.0)*
Average
NDMA
(pg/m3)
3.1
4.6
Average
NDMA
(Mg/0.5hr)
4.6
9.2
NMOR
(yg/m3)
N.D.
N.D.
0.3
N.D.
Average
NMOR
(Ug/m3)
N.D.
0.1
Average
NMOR
(vg/0.5hr)
N.D.
0.3
NO.N02x 10 12
2.5
4.8
NDMA(yg/0.5hr)
NO.N02
1.2
0.9
x 10-12
N.D. - Not Detected
* - HPLC-TEA confirmation
-------
Figure Captions:
Figure 4-a
Figure 4-b
Figure 4-c
Figure 4-d
III-20
GC-TEA Chromatogram of 4 ng NDMA Standard.
GC-TEA Chromatogram of a Crankcase Emission Sample Showing the
presence of 25.3 yg/m-^ of NDMA.
HPLC-TEA Chromatogram of 10 ng NDMA Standard.
HPLC-TEA Chromatogram of a Crankcase Emission Sample Showing
the presence of 26.8 yg/m^ of NDMA.
The sample was collected from Mack ETAY(B) 673A engine operating with Mobil
Delvac Super 15W40 oil in mode number 1.
-------
OQ
i-i
(I
Fl
-NDMA
ATTENUATION 16
NDMA
ATTENUATION 8
— NDMA
-i.
NDMA
ATTENUATION 8
ATTENUATION 8
H
H
I
N5
-------
Figure Captions:
Figure 5-a
Figure 5-b
Figure 5-c
Figure 5-d
111-22
GC-TEA Chroraatogram of 4 ng NDMA Standard.
GC-TEA Chromatogram of a Crankcase Emission Sample Showing the
presence of 6 yg/nH of NDMA.
HPLC-TEA Chromatogram of 16 ng NDMA Standard.
HPLC-TEA Chromatogram of a Crankcase Emission Sample Showing
the presence of 6 Ug/m^ of NDMA.
The sample was collected from DDAD 6V-71N engine operating with Mobil Delvac
Super 15W40 oil in mode 5.
-------
(a)
(c)
a
z
CO
|
(b)
6420
TIME (MINUTES)
111-23
oo
z
o
b
13
III!
(d)
Q
Z
<*•
z
O
UJ
£
6420
TIME (MINUTES)
Figure: 5
-------
111-24
Figure Captions:
Figure 6-a GC-TEA Chromatogram of 4 ng NDMA Standard.
Figure 6-b GC-TEA Chromatogram of a Crankcase Emission Sample Showing the
presence of 6.7 yg/m^ of NDMA.
Figure 6-c HPLC-TEA Chromatogram of 10 ng NDMA Standard.
Figure 6-d HPLC-TEA Chromatogram of a Crankcase Emission Sample Showing
the presence of 6.4 yg/m-* of NDMA.
The sample was collected from Caterpillar 3406 engine operating with Mobil
Delvac Super 15W40 oil in mode 5.
-------
d *
m *
g;
z ro
c
n ,-,
£2
hrj ""'
H-
OT
h!
ro
-l
420
IME (MINUTES)
6
cr
~ V^ NDMA
-V
ATTENUATION 4
L ?
_ S ATTENUATIONS
o
~ L NOMA
-v
Jia-
ATTENUATION 8
_ ^ t.
1 NOMA
-' ATTENUATIONS
I
N3
U1
-------
Table 10
Confirmation of NMOR on GC-TEA and HPLC-TEA
111-26
No.
Engine
Oil
GC-TEA
(ppm)
HPLC-TEA
(ppm)
1 Mack CTAY (B) 673A Mobil Delvac 0.63 0.65
Super 15 W 40
2 Mack ETAY (B) 673A Mobil Delvac 1200 0.90 0.85
3 Mack ETAY (B) 673A Amoco 300 SAE 30 0.10 0.10
-------
111-27
Figure Captions:
Figure 7-a
Figure 7-b
Figure 7-c
Figure 7-d
GC-TEA Chromatogram of 2 ng NMOR Standard.
GC-TEA Chromatogram of Combined Crankcase Emission Samples
showing the presence of 0.63 ppm of NMOR in solution.
HPLC-TEA Chromatogram of 5 ng NMOR Standard.
HPLC-TEA Confirmation of the combined Crankcase Emission
Samples showing the presence of 0.65 ppm of NMOR in solution.
The samples were collected from Mack ETAY (B) 673A engine operating with Mobil
Delvac Super 15W40 oil in modes 3 through 7 and then combined to increase the
detect ion.
-------
ca
z
b)
09
I
§
o:
o
111-28
d)
cc
z
16 14 12 10 8 6 4 2
TIME (MINUTES)
0 14 12 10 8 6 4 2
TIME (MINUTES)
Figure: 7
-------
111-29
Figure Captions:
Figure 8-a GC-TEA Chromatogram of combined Crankcase Emission Samples
showing the presence of 0.90 ppm of NMOR in solution.
Figure 8-b HPLC-TEA confirmation of the combined Crankcase Emission
Samples showing the presence of 0.85 ppm of NMOR in solution.
The samples were collected from Mack ETAY (B) 673A engine operating with Mobil
Delvac 1200 oil in modes 3 through 7 and then combined to increase the
detect ion.
Figure 9-a GC-TEA Chromatogram of combined Crankcase Emission Samples
showing the presence of 0.10 ppm of NMOR in solution.
Figure 9-b HPLC-TEA confirmation of the combined Crankcase Emission
Samples showing the presence of 0.10 ppm of NMOR in solution.
The samples were collected from Mack ETAY (B) 673A engine operating with Amoco
300 SAE 30 oil in modes 3 through 7 and then combined to increase the detection.
-------
111-30
(Bo)
(9o>
J I L
18 16 14 12 10 6 6 4
TIME (MINUTES)
«Bb>
(9b)
2 0 16 14 12 10 8 6
TIME (MINUTES)
Top Figure: 8
Bottom Figure: 9
-------
111-31
were operated in parallel using different lengths of tubing between the
crankcase and traps (I1 vs. 6.5"). There was no increase in the levels of NDMA
or NMOR with the longer sampling line. Checking for the formation of
nitrosamines in the first few inches of sampling line was not deemed necessary
since trucks normally release emissions through 2 to 3 feet of exhaust pipe.
The identity of NDMA from the liquid traps was established by observing the
same quantitation at the appropriate chromatographic retention time on both GC
and HPLC-TEA (see Tables 3-9 and Figures 4-6). Further confirmation was
obtained by combining the liquid trap extracts from a single engine,
concentrating to 1 ml, and examining the concentrate by GC-high resolution MS
(see Appendix D for comparison of GC-TEA, GC-MS results).
The confirmation of NMOR on GC-MS could not be obtained due to the lack of
sufficient amount of material. It's presence was confirmed on GC-TEA, HPLC-TEA
on the combined samples from a single engine (see Table 10 and Figure 7, 8, 9).
2. Tests with ThernoSorb'"/N Air Samplers and Sulfamic Acid Cartridges
As with the aqueous traps, recovery studies were conducted using a mixture
containing 500 ng ech of NDMA, NDEA, NDPA, NDBA, NPiP, NPYR and NMOR. Three
separate experiments were conducted; first with the ThermoSorbt"/N Air Sampler
alone, second with an empty cartridge folowed by a ThermoSorbI"/N Air Sampler,
third with a cartridge filled with sulfamic acid followed by a ThermoSorb'"/N Air
Sampler. The results, shown in Table 11, indicate that in spite of the pentane
and DCM/pentane wash, 77 to 86% of the nitrosamines are recovered in the acetone
fraction. By comparison, if acetone alone had been used, the recovery would
have been 98-100% (Rounbehler, D.P. et_ al_. , 1980). The 'dead space' in an empty
cartridge led to another 20 to 30% loss in recovery. Recovery with and without
sulfamic acid in the cartridge was virtually identical.
-------
111-32
ThermoSorb™/N Air Samplers have been tested for breakthrough, using the 7
test nitrosamines (Rounbehler, D.P. e_t_ jiK , 1980). Even after passing 2000 L of
air at 2 L/min and 25°C through the cartridges, breakthrough was not observed.
Resistance to breakthrough was confirmed by using two ThermoSorb samplers
in series during actual engine sampling. No detectable amounts of nitrosamines
were found in the second cartridge. The stability of nitrosamines in the
ThermoSorb samplers has been tested by the suppliers, and no significant losses
were found even after 5 weeks of storage at room temperature (Rounbehler, D.P.
and Reisch, J.W., 1979, unpublished results).
As with the liquid traps, the possibility that nitrosamines could be formed
artifactually during collection and/or analysis, was tested both in the
laboratory, and during tests on a diesel engine. For the laboratory simulation,
a solution containing 1 part-per-thousand (by weight) of each amine, DMA,
dipropylamine (DPA), Pip, PYR and MOR was introduced into the sulfamic acid
cartridges at 6 rain intervals (see Figure 10) for 1 hr. One cartridge received
a total of 25 pg of each of the amines; the other cartridge received a total of
50 yg of each of the amines. The gas phase consisted of 100 ppm NO + 7ppm N02
in air; with the total NOX passed over the cartridges during the run being 12
rag NO + 0.8 mg N02• Extraction of the ThermoSorbm/N Air Sampler, using
techniques previously described and subsequent analysis, showed that in only one
experiment was a trace of NMOR observed (see Table 12). The yield of NMOR
observed (see Table 12). The yield of NMOR was approximately 0.03%, with the
amount being observed virtually identical to the detection limit. For the other
experiments, nitrosamines were not observed.
For the artifact tests on a diesel engine, only MOR was used, because it
had been shown that MOR has the highest nitrosation rate with NOX on solid
-------
111-33
Table 11
Recoveries of Various Nitrosamines
(500 ng each) from Sulfamic Acid and ThermoSorbw/N Air Samplers
Nitrosami ne
TiiermoSorb'"/N
Air Sampler
% Recovery
Empty Catridge
and
ThermoSorb'VN
Air Sampler
% Recovery
Sulfamic Acid
and
ThermoSorb'VN
Air Sampler
% Recovery
NDMA
NDEA
NDPA
NDBA
NPiP
NPYR
NMOR
77
78
79
75
81
86
83
57
55
56
54
58
55
53
61
51
44
42
53
57
58
* The recovery is the average of two measurements.
-------
111-34
adsorbers (Goff, U.G. and Coombs, J.R. , 1979, unpublished results) when compared
with DMA, DPA, Pip and PYR. Fifty yg of MOR was introduced into the sulfamic
acid cartridge at the beginning of the test. For one of the tests, additional
nitrogen oxides such as 80 ppm NO and 6 ppm N02 (total added was 5.4 mg NO and
0.4 mg N02) were passed through the cartridges. The results, shown in Table
13, show that NMOR was not detected in any of the tests.
TASK II AND III. Engine Selection and Testing
The sample collection and preparation methods described in Section III. C,
Task I were used to collect and analyze crankcase emission samples. The
influence of the engine type was addressed by taking samples from three
different heavy duty engines operated with the same type of oil and the
influence of the oil type was considered by taking crankcase emission samples
from the same heavy-duty engine after operation with four different oils. Also
a LD diesel engine was sampled to see if it behaves similarly to HD diesel
engines in producing nitrosamines. Mack ETAY (B) 673A engine crankcase
emissions were sampled with Shell Rotella T SAE 30, Amoco 300 SAE 30,
Mobil-Delvac 1200 SAE 30, Mobil Delvac Super 15-W-40 oils in separate runs.
Other engines were samples with only Mobil Delvac Super 15-W-40 oil in the
crankcase. Duplicate samples were taken and the results were averaged for each
mode of the engine. The nitrosamine amounts were expressed as concentration
(yg/nH), and as mass flow (yg/1/2 hr) versus the product NO and N02
concentrations in the crankcase emissions. These results are presented in
Tables 3 through 9.
-------
NOX Source
\
1000 ppm NO
70 ppm NO2in N2
Air Bleed and
Amine Injection
Air Bleed and
Amine Injection
100 ppm NO
7 ppm NO2 in N2 and Air
Sulfamic
Acid
Cartridge
Sulfamic
Acid
Cartridge
ThermoSorb™/N
Air Sampler
ThermoSorb™/N
Air Sampler
TM
Figure : 10 Simulated Engine Run with Sulfamic Acid, ThermoSorb /N Air Sampler
Sampling Pump
2L/min
Sampling Pump
2L/min
i
w
Ui
-------
111-36
Table 12
Results of Artifact Experiments with Sulfamic Acid and
ThermoSorb"l/N Air Sampler Under Simulated Engine Conditions
Added Amine
Nitrosamine Detected
Detection Limit
( yg/cartridge)
25 & 50 yg Dimethylamine
25 & 50 yg Dimpropylamine
25 & 50 yg Piperidine
25 & 50 yg Pyrrolidine
25 yg Morpholine
50 yg Morpholine
None
None
None
None
None
0.016 yg NMOR*
0.006
0.012
0.016
0.016
0.016
0.016
*The amount observed was at the detection limit.
-------
111-37
Table 13
Results of Artifact Experiments with Sulfaraic Acid and
ThermoSorbIM/N Air Sampler Under Actual Engine Conditions
Experiment
A
B
Q**
Added
Ami ne*
50 yg
morpholine
50 yg
morpholine
50 yg
morpholine
Flow Rate
(L/min)
2.3
2.2
2.2
Time
(hr)
0.5
0.5
0.5
Nitrosamine
Detected
None
None
None
Detection Limit
(yg/sampler)
0.018
0.018
0.018
* The amine was added to the sulfamic acid trap; nitrosamines were looked for
in the following ThermoSorbIH/N Air Sampler trap.
** This sample received extra NO + N02 (see text).
-------
111-38
TASK IV. Oil Analysis Method Development for Nitrosamine
These analyses were carried out by bubbling air at 0.5 L/min. for one hour
through a 50 g oil sample which was maintained at 110°C. Ascorbic acid (0.5 g
in 1 ml water) and DL-a-tocopherol were added to the oil to inhibit in situ
nitrosation (Mergens, W.J. et_ al_. , 1978; Archer, M.C. &t_ a}_. , 1975; Fiddler, W.
et al., 1973). The apparatus used is shown in Figure 11. Nitrosamines were
collected on a ThermoSorb™/N Air Sampler, and eluted as described earlier (see
Figure 2). An aliquot of the acetone fraction was introduced into the GC-TEA
and/or HPLC-TEA for analysis.
Artifact Control Experiments
A recovery study was conducted by adding a mixture of nitrosamines at 1
part-per-billion (ppb) and 10 ppb levels to a nitrosamine-free oil sample. The
recovery data and detection limits of nitrosamines in the oil are shown in Table
14. A GC-TEA chromatogram of the spiked sample, Figure 12, is also attached.
The recoveries from oil samples spiked at 1 ppb level were lower than the
recoveries at 10 ppb level. The lower recoveries might be attributed to
systematic errors. The possibility of artifactual formation of nitrosamines
during the analysis was also checked. Five amines, DMA, DPA, PiP, PYR, and MOR
(50 yg each), were added to a nitrosamine-free oil and the oil was analyzed as
in the test samples. In no case was the nitrosamine derivative found to be
present. In a second test, 50 yg of each amine was added to the ThermoSorb™/N
Air Sampler and the experiment repeated. Again, no trace of the nitrosamine
derivative could be detected. The absence of any nitrosamine peak in these
experiments also proves that the air and ThermoSorbIM/N Air Sampler used
contained no preformed nitrosamines. The air used was checked for the presence
of nitrosating agents by placing a morpholine spiked (50 yg) ThermoSorb^/N Air
-------
OQ
c
O
CO
I
n
o
o
rt
H-
o
3
ee-in
-------
Table 14
Recovery of Various Nitrosamines
From Oil Samples
111-40
Nitrosamine
Recovery (%)*
10 ppb 1 ppb
Detection Limit in Oil
(ppb)
Nitrosodimethylamine 73
48
0.1
Nitrosodiethylamine '77
40
0.2
Nitrosodipropylamine 56 34
0.3
Nitrosodibutylamine 25
28
1.0
Nitrosopiperidine
47 22
0.7
Nitrosopyrrolidine
55 34
0.4
Nitrosomorpholine
66 42
0.5
*Average of two measurements
-------
111-41
Figure Captions:
Figure 12-a GC-TEA Chromatogram of 2 ng mixture of NDMA, NDEA, NDPA,
NDBA, NPiP, NPYR, and NMOR.
Figure 12-b GC-TEA Chromatogram of an Oil Sample to Which a Standard
Mixture of 7 nitrosamines (NDMA, NDEA, NDPA, NDBA, NPiP, NPYR,
NMOR) had been added, each at the 1 ppb level.
-------
i—i—r
I
I
I
I
111-42
LU
O
12 10 8 6 42
TIME (MINUTES)
(b)
14 12 10 8 6 4 2
TIME (MINUTES)
(a)
Figure: 12
-------
111-43
Sampler at the air inlet of the flask. There was no formation of NMOR
(detection limit: 0.016 pg per sampler).
A stability study of nitrosamines in oils was conducted by analyzing
different portions of the same oil which were exposed to different conditions.
The results are given in Table 15. Although the results for Mobil Delvac 1200
obtained at 42nd hr of usage are not significantly different, the data from 65th
hr sample might suggest that some nitrosamine deterioration is occuring under
storage conditions, but not enough samples were available for analysis to permit
any statistically significant results.
TASK V. Selection and Survey of the Oil Samples
A nitrosamine survey of unused and used oils was conducted. Unused oils
were surveyed to determine the effect of the oil type and different additives.
These oils were supplied by oil companies and SWRI or purchased by the New
F.ngland Institute for Life Sciences. The oils supplied by SWRI were taken from
various barrels and quart cases from their in-house stock and shipped to us by
Federal Express. The samples obtained by the New England Institute for Life
Sciences were purchased in quart size cans. Oil samples obtained from oil
companies were requested by the EPA project officer and shipped to us in pint
and quart size cans.
Used oil samples were surveyed to determine the effect of the usage
duration on the nitrosamine levels. These samples were supplied by the engine
manufacturers upon request by the EPA project officer. They were collected
after various intervals of usage and shipped in pint size cans or plastic
containers via UPS, Emery Air Freight or Federal Express and were refrigerated
upon arrival at our laboratories. The information supplied by the various
engine manufacturing and oil companies is given in Appendix E.
-------
HI-44
Some used oil samples were acquired by the New England Institute for Life
Sciences from auto service and repair stations and gas stations around the
Boston area. 100 ml plastic bottles were left with the cooperating station and
then picked up in 1-6 days. They were refrigerated upon receipt.
Except for the Amoco 300 SAE 30, the oils that were used in SWRI engines
for crankcase emissions testing were acquired in Texas by SWRI. The Amoco oil
was supplied by Amoco Oil Company from their Whiting refinery in Chicago.
We initially obtained some oil from Amoco Houston refinery to be used in
SWRI test engines. Nitrosation of this oil produced (Table 16, Sample NO. 46)
much less amounts of NDMA as compared to the one obtained from Amoco Whiting
refinery (Table 16, Sample No. 11). For that reason, Amoco 300 SAE 30 (Table
16, Sample No. 59) was obtained from Whiting refinery at the time of SWRI engine
testing. The difference between the two can be explained by the different
additive package used in these oils.
Oil analysis methods described in Section III, Task IV were used for
determining the volatile nitrosamine levels in the used and unused oils. The
results are given in Table 16. The results of the used oil samples acquired by
the New England Institute for Life Sciences are given in Appendix F. Later
results must be regarded cautiously since the origin and handling of the samples
could not be supervised.
TASK VI. Oil Nitrosation Method
This method was developed so as to simulate the nitrosation conditions
which may be occuring in a typical engine. Using nitrogen oxides as the
nitrosating agent, amines present in the oil would be nitrosated to give their
corresponding nitrosamines. Fifty gram samples of used or unused oils were
heated for one hour at 110°C while a gas mixture containing 100 parts-per-bil-
lion (ppm) NO + 7 ppm N02 in nitrogen was bubbled through at a rate of 2 L/min
(12 mg NO + 0.8 mg N02 total introduced into the samples). Nitrosation
inhibitors were not added to the oil. Nitrosamines were collected on
(cont. on pg. IV-1)
-------
111-45
Table 15
Stability of NDMA in Oil Under Different Conditions
Oil Condition
Mobil Delvac 1200, 42* analyzed upon receipt
" refrigerated for 2 days
kept at room temperature
NDMA (ppb)
GC-TEA
1.5
1.4
1.6
(R.T.) for 2 days
" " heated at 50-55°C for 75 min. 1.8
0.5 p,m ascorbic acid + 100 mg 1.6
DL ot-tocopherol and kept at
R.T. for 2 days
Mobil Delvac 1200, 65** analyzed upon receipt 2.0
refrigerated for 10 days 1.9
" " kept at R.T. for 10 days 1.5
* This oil was analyzed after being in test engine (Mack 676 ENDT) for 42 hours,
r
**This oil was analyzed after being in test engine (Mack 676 ENDT) for 65 hours,
-------
Oil Analysis
Table 16
and Nitrosation Results
As Received
Sample
2
3
7
8
11
13
14
46
9
10
12
20
No. Oil
NDMA
(ppb)
GC-TEA
NMOR
(ppb)
GC-TEA
Nitrosated
NDMA
(ppb)
GC-TEA
NMOR
(ppb)
GC-TEA
Oils Supplied by SWRI
Mobil Delvac 1230 SAE 30
Texaco Ursa Super 3 SAE 30
Gulf Lube X.H.D. SAE 30
Chevron Delo 300 SAE 30
Amoco 300 SAE 30
Shell Rotella 30
Shell Rotella T. 15-W-40
Amoco 300 SAE 30 (b)
Oils Obtained by New England Inst
Mobil Delvac 1200 SAE 30
Volvo line SAE 30
Mobil Heavy Duty SAE 30
Chevron Delo 400 SAE 30
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
itute for
N.D.
N.D.
N.D.
N.D.
N.D
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
22.0(22.0)(a)
8.0
3.6
0.8
54.0(54.0)(a)
2.4
1.0
11.8
Life Sciences Around Boston
N.D.
N.D.
N.D.
N.D.
18.0
2.0
36.0(29.0)(a)
1.6
4.0(4.3)(a)
1.5
2.1
N.D.
2.4(a)
5.6
1.4
N.D.
Area
N.D.
0.8
2.4
N.D.
Gasoline Engine Oils Obtained by New England Institute for Life Sciences Around Boston Area
47
48
49
50
51
52
53
54
55
Texaco Havolin SAE 30
Citgo Multigrade SAE 30
Gulf pride Multi 6 10W-20W-40
Quaker State 10-W-40
Pennzoil Multi-Vis SAE 10-W-30
Mobil Special 10-W-30
Exxon Uniflo 10-W-40
Shell Fire and Ice 10-W-40
Mobil Super 10-W-40
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
24.0
N.D.
21.0
2.7
N.D.
17.4
1.1
18.5
38.0
1.2
N.D.
2.4
1.2
N.D.
3.3
N.D.
13.7
2.4
Footnotes to Table 16:
(a)
(b)
(c)
(d)
Confirmed on HPLC-TEA.
Amoco oil from Houston Refinery.
Amoco oil from Whiting Refinery in Chicago.
Base oil stock. Since nitrosation of this base oil
stock did
not produce
any nitrosamines
, it suggests
that the nitrosamines produced in oils are being produced as a result of the oil additives.
-------
Table 16 (cont.)
Oil Analysis and Nitrosation Results
Sample No.
Oil
As Received
NDMA NMOR
(ppb) (ppb)
GC-TEA GC-TEA
Oils Obtained by New England Institute for Life Sciences
4
15
75
1
6
5
16
Shell Rotella T Premium
Multi-Purpose SAE 30
Oils Supplied
Amoco 300 SAE 15-W-40
Amoco HX 40(d)
Amoco 300 SAE 30
Amoco 200 SAE 30
Oils Supplied
Arco Fleet S-3 plus SAE 30
Arco Fleet S-3 plus 15-W-40
N.D.
by Amoco(c)
0.35
N.D.
N.D.
N.D.
by Arco
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
Nit rosated
NDMA NMOR
(ppb) (ppb)
GC-TEA GC-TEA
in Arizona
1.8
6.2
N.D.
64.0(59)(a)
3.1
4.8
2.0
N.D.
N.D.
N.D.
2.8(2.
N.D.
N.D.
3.3
Oils Supplied by Volvoline Oil Company
17
18
19
21
22
43
Volvoline 15W-20W-40 All Fleet
Volvoline SAE 30 All Fleet
Volvoline HD Super HPD SAE 30,
Detergent
Oils Supplied by Mobil
Mobil Delvac 1230
Mobil Delvac Super 15-W-40
Mobil Delvac 1
N.D.
N.D.
N.D.
Oil Corporat
N.D.
N.D.
0.45
N.D.
N.D.
N.D.
ion
N.D.
N.D.
N.D.
C.S
1.6
N.D.
15.0
39.0(42.0)(a)
2.4
N.D.
N.D.
N.D.
7.7
1.0
N.D.
-------
Table 16 (cont.)
Oil Analysis and Nitrosation Results
Sample No.
23
24
25
26
27
28
29
30
31
34
32
33
37
38
39
40
Oil
As Received
NDMA NMOR
(ppb) (ppb)
GC-TEA GC-TEA
Nitrosated
NDMA NMOR
(ppb) (ppb)
GC-TEA GC-TEA
Oils Supplied by Exxon
Exxon HDX Plus 30
Exxon XD-3-30
Exxon 2118-S-3; 15-W-40
Oils Supplied by Gulf
Gulf Super Duty 30 LS-8645
Gulf Lube X.H.D. 10-W-30 LS-8648
Gulf Super Duty 15-W-40 LS-8646
Gulf Lube X.H.D. 30 LS-8647
Oils Supplied by
Chevron Delo 100 SAE 30
Chevron Delo 200 SAE 30
Chevron Delo 300 SAE 30
Chevron Delo 400 SAE 30
Chevron Delo 400 15-W-40
Oils Supplied by
Texaco Ursa Super 3 SAE 30
Texaco Ursa Extra Duty SAE 30
Texaco Ursa Super Plus SAE 30
Texaco Ursa Plus 15-W-40
N.D.
N.D.
N.D.
Oil Company
N.D.
N.D.
N.D.
N.D.
Chevron
N.D.
N.D.
N.D.
N.D.
N.D.
Texaco
3.7
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
1.0
1.4
0.8
1.3
0.8
1.3
0.7
0.5
1.2
1.0
N.D.
5.4
4.8
1.1
1.2
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
0.5
2.4
.p-
oo
-------
Table 16 (cont.)
Oil Analysis and Nitrosation Results
Sample No.
Oil
As Received
NDMA NMOR
(ppb) (ppb)
GC-TEA GC-TEA
Nitrosated
NDMA NMOR
(ppb) (ppb)
GC-TEA GC-TEA
Oils Used in SWRI Engines
44
60
59
61
45
62
58
63
64
65
66
35
41
42
36
Fresh Shell Rotella T SAE 30
Used Shell Rotella T SAE 30
(8.6-hr sample; Mack)
Fresh Amoco 300 SAE 30 (c)
Used Amoco 300 SAE 30
(6.6-hr sample; Mack)
Fresh Mobil Delvac 1200 SAE 30
Used Mobil Delvac 1200 SAE 30
(6.0-hr sample; Mack)
Fresh Mobil Delvac Super 15-W-40
Used Mobil Delvac Super 15-W-40
(7.2-hr sample; Mack)
Used Mobil Delvac Super 15-W-40
(5.5-hr sample; DDAD)
Used Mobil Delvac Super 15-W-40
(5.6-hr sample; Cat)
Used Mobil Delvac Super 15-W-40
(3.0-hr sample; Mercedes)
Oils Supplied by Deutz
Fresh Shell Rotella S 30
Used Shell Rotella S 30
(75.5-hr; sample)
Used Shell Rotella S 30
(154.2-hr; sample)
Used Shell Rotella S 30
(I66.0.hr; sample)
N.D.
N.D.
N.D.
0.2
N.D.
0.4
N.D.
0.8
0.1
0.4
0.8
Diesel
N.D.
0.8
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
Limited
N.D.
N.D.
N.D.
N.D.
0.8(0.8)(a)
0.6(0.8)(a)
25.0(24.0)(a)
3.0(a)
88.2(82.0)(a)
5.7
202. 0(191. 0)(a)
15.0
42.2
12.7
48.4
2.6
1.4
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
25.4
1.5
23.5
3.3
11.2
5.4
8.8
156.0
2.0
0.3
0.4
-p-
-------
Table 16 (cont.)
Oil Analysis and Nitrosation Results
Sample No.
71
73
72
74
Oil
Oils Supplied by Detroit
Fresh Texaco Ursa ED 30
Used Texaco Ursa ED 30
(75-hr; sample)
Used Texaco Ursa ED 30
(150-hr; sample)
Used Texaco Ursa ED 30
(217-hr; sample)
As Received Nitrosated
NDMA NMOR NDMA NMOR
(ppb) (ppb) (ppb) (ppb)
GC-TEA GC-TEA GC-TEA GC-TEA
Diesel All
N.D.
N.D.
N.D.
N.D.
Oils Supplied by Caterpillar Tractor
79
80
81
82
83
84
85
86
87
89
90
Fresh Chevron RPM Delo 300 (30W)
Used Chevron RPM Delo 300 (30W)
(75-hr; sample)
Used Chevron RPM Delo 300 (30W)
(150-hr; sample)
Used Chevron RPM Delo 300 (30W)
(250-hr; sample)
Fresh Amoco 300 15-W-40
Used Amoco 300 15-W-40
(50-hr; sample)
Used Amoco 300 15-W-40
(75-hr; sample)
Used Amoco 300 15-W-40
(150-hr; sample)
Fresh Chevron RPM Delo 400 (30W)
Used Chevron RPM Delo 400 (30W)
(150-hr; sample)
Used Chevron RPM Delo 400 (30W)
(250-hr; sample)
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
0.2
N.D.
N.D.
N.D.
0.4
ison
N.D. N.D. N.D.
N.D.
N.D.
N.D. N.D. N.D.
Company
N.D. 0.6 N.D.
N.D.
N.D.
N.D. N.D. N.D.
N.D. 1.7 N.D.
N.D.
N.D.
N.D. N.D. N.D.
N.D. N.D. N.D.
N.D.
N.D. N.D. N.D.
H
I
-------
Table 16 (cont.)
Oil Analvsis and Nitrosation Results
Sample No.
Oil
As Received
NDMA NMOR
(ppb) (ppb)
GC-TEA GC-TEA
Nitrosated
NDMA NMOR
(ppb) (ppb)
GC-TEA GC-TEA
Oils Supplied by Mack Truck, Inc.
76
77
78
91
92
•
67
68
69
70
93
94
95
96
Fresh Mobil Infilrex 205
Used Mobil Infilrex 205
(75-hr; sample Unit 212)
Used Mobil Infilrex 205
(75-hr; sample Unit 211)
Used Mobil Infilrex 205
(150-hr; sample Unit 211)
Used Mobil Infilrex 205
(300-hr sample; Unit 212)
Oils Supplied by Cummins
Fresh Shell Rotella T
Used Shell Rotella T
(5749 mi on oil)
Used Shell Rotella T
(11,427 mi on oil)
Used Shell Rotella T
(15,000 mi on oil)
Fresh Chevron Delo 100 30W
Used Chevron Delo 100 30W
(6000 mi on oil)
Used Chevron Delo 100 30W
(11000 mi on oil)
Used Chevron Delo 100 30W
(15000 mi on oil)
N.D.
0.2
0.3
N.D.
N.D.
Engine Company
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
, Inc .
N.D.
N.D.
N.D.
N.D.
N.D.
—
N.D.
-
161.0
1.1
N.D.
_
N.D.
N.D.
N.D.
N.D.
53.3
N.D.
N.D.
N.D.
0.9
13.3
N.D.
N.D.
_
N.D.
N.D.
N.D.
N.D.
1.2
5.4
N.D.
N.D.
N.D.
-------
IV-1
ThermoSorb'"/N Air Sampler attached to the gas outlet of the oil containing flask
and eluted using the procedures described above (see Figure 2).
TASK VII. Survey of the Nitrosability of the Oils
Using the method in section III, Task VI, unused and used oil samples were
nitrosated. The results are given in Table 16. This technique was used to
correlate the nitrosation potential of the oil with the actual nitrosamine
emissions from the diesel engine crankcase (see Table 17, Figure 13).
IV. DISCUSSION OF RESULTS
Tt has been conclusively shown that the analytical methods developed here
for the analysis of crankcase emissions were not prone to artifacts. It has
been demonstrated that even the presence of nitrosamine precursors in the traps
in relatively large amounts did not produce nitrosamines, both under normal
engine test conditions, and also under artificially elevated NOX levels.
The absence of any nitrosamines in simulation experiments also proved that
the traps didn't contain any preformed nitrosamines or their precursors that
might nitrosate under engine sampling conditions.
NDMA levels were the same (within experimental error) in pH 4 phosphate
citrate buffer traps and in sulfamic acid/ThermoSorb"l/N Air Samplers when
sampling was done using these traps in parallel on actual crankcase samples (See
Tables 3-9 for the results of parallel sampling with pH 4 phosphate citrate
buffer traps and sulfamic acid/ThermoSorb"YN Air Samplers.) Such duplication
of the NDMA levels in completely different trapping systems is further
indication that the two techniques are artifact free.
The detection limit for both trapping methods was about 100 yg/m^ for 60L
of crankcase emission samples. The nitrosamines that were extracted from the
traps were analyzed on GC-TEA and HPLC-TEA. Analysis on both systems serves as
a good confirmatory technique. In GC, nitrosamines elute as a function of their
-------
IV-2
Table 17
Oil NDMA in Nitrosated Oil (ppb) Average NDMA* in emission (yg/0.5 hr)
1 1 2
2 25 18
3 88 48
4 200 72
Oil 1 Shell Rotella T SAE 30
2 Amoco 300 SAE 30
3 Mobil Delvac 1200 SAE 30
4 Mobil Delvac Super 15 W 40
* NDMA levels were measured in Mack ETAY (B) 673A engine.
** r (correlation coefficient), was obtained from the least-squares linear
regression analysis of the two variables, namely NDMA in nitrosated oils and
averaged NDMA in emissions.
-------
IV-3
Figure Captions:
Figure 13 Correlation between the NDMA levels in the nitrosated
oils and in the crankcase emissions from Mack ETAY (B)
673A engine.
-------
50
75
100 125 150
NDMA IN NITROSATED OIL (ppb)
Figure: 13
175
200
225
H
-------
IV-5
relative vapor pressures, and solubility in the liquid phase. In HPLC, the
nitrosamines generally elute according to their polarity, solubility in the
liquid phase, and/or ionic properties. Because of the difference in these
physical properties, the elution order of a series of compounds by GC and HPLC
is different. If a selective detector such as the TEA is used for both GC and
HPLC, the possibility of a coeluting peak giving a response in both systems is
extremely small. Identification is considered positive if two criteria are met:
1) a single peak eluting at the known GC retention time of a standard is
observed and 2) the magnitude of the GC-TEA and HPLC-TEA peaks are identical.
See Tables 3 through 9 and Figures 4 through 9 for the GC-TEA and HPLC-TEA
confirmation of NDMA and NMOR peaks. Further confirmatory evidence as to the
identity of the nitrosamines was obtained by GC-high resolution MS (See Appendix
D).
Nitrosamine levels in the crankcase emissions will be discussed according
to the effects of three variables: nitrogen oxide levels in the crankcase
emissions, amine levels in the oils and the effects of crankcase flow rates.
Other influential engine variables can't be pinpointed at this time but there is
some evidence that they exist. Obviously amines in the oils and the nitrogen
oxides in the emissions are the main parameters, and, depending on the type of
oil and type of engine used, one or the other can be the limiting factor in
determining the nitrosamine levels.
Nitrosation of oil samples before and after use in the SWRI test engines
indicated that used oils did not as readily produce nitrosamines as the corre-
sponding unused oils (see Table 16, Oils Used in SWRI Engines). This result
suggests that the nitrosamine precursors in the oil are somehow used up
-------
IV-6
or otherwise removed from the process. Since production of nitrosamines from
nitrosated oils suggests that the nitrosamine precursors in the oil are the main
source of nitrosamines found in crankcase emissions, then one would expect a
decrease in crankcase emission nitrosamine concentrations as the time the oil
has been in the crankcase increases and, correspondingly, the nitrosability of
the oil decreases (see Table 16).
According to the data obtained from the engine crankcase emissions however,
this reduction of nitrosamine concentration in the emissions as a function of
the operating times of the experiments did not occur (see Tables 3 through 9,
last column). This observation might suggest that amine amounts available for
nitrosation was not a limiting factor in most engine runs of the duration used.
During method development, the engine was sampled at different times, but
an attempt to draw any conclusions from those results were avoided since the
engine variables were not controlled. Nitrosamine measurements taken during
method development are given in Appendix G.
If we look at the nitrosamine levels of each engine irrespective of NO and
N02 concentrations (nitrosamines/NO.NC^)} it is observed that the
nitrosamine amounts produced per NO.NC>2 is highest for idle case which corres-
ponds to the lowest crankcase flows. This observation suggests that the time of
contact is important and in cases of low flow (and consequently longer contact
time cases between the NO,, and the amines in the oil) the nitrosamine levels
A.
produced are higher. Thus the nitrosamine levels are probably limited by the
contact time.
Usually the nitrosamine amount produced per NO.N02 is high for the first
mode of the engine run which could be attributed to the low flow rates
-------
IV-7
associated with this mode or to carry over from nitrosamines produced during 1
hr engine warm up time.
If we compare the ratios of NDMA/NO.N02 in different engines using the
same oil (namely DDAD, Mack, Caterpillar with Mobil Delvac Super 15-W-40 oil) we
will be comparing nitrosamine levels irrespective of NO.N02 concentrations and
oil type (see Tables 3 through 9, last column). The high value of NDMA/NO.N02
in the Detroit Diesel engine can be explained by the lowev crankcase flows all
through the modes and higher contact time between the NO,, and the nitrosamine
2v
precursors. See Appendix C, Table 6 for flows of heavy duty engines & Table 16
for the crankcase flow of light duty engine.
Comparison of NDMA/NO.N02 levels in Mack and Caterpillar suggests an
engine parameter other than the crankcase flow rates is involved in determining
the nitrosamine levels since, the flow rates for these two engines are quite
similar. (See Appendix C, Table 6 for flows).
Correlation analysis between the crankcase nitrosamine levels (yg/0.5 hr)
and NOX, N02, (N02)2, NO.N02 (the multiple of NO and N02),
NO.N02/T (T = the temperature in degrees Kelvin) were made and correlation
coefficients (r) and determination coefficients (r^) were calculated to obtain
a measure of the degree of association between the above variables. In most
cases the r values between the nitrosamine levels and NO.N02 were highest as
compared to NOX, N02, NO2, NO.N02/T. These r values were around 0.8,
0.9 which indicates a fairly strong linear relationship between the two (see
Tables 18 and 19).
The oil analysis procedure developed here is a new concept in nitrosamine
analysis. It is efficient, and again has been shown to be artifact free. It
should be noted that the recovery rates are affected by a number of factors,
-------
IV-8
for example, when samples were spiked at the 1 ppb level, the recoveries for
NDMA were around 50%. Spiking samples the 10 ppb level however, resulted in
recoveries as high as 80%. Other experimental conditions such as gas flow rate
and the sample temperature also affect the recoveries. For this reason,
whenever this method is utilized, the recoveries should be determined for the
exact set of conditions used during the analysis.
Most of the used and unused oil samples that were analyzed in the as
received condition did not contain any volatile nitrosamines (detection limit
NDMA: 0.1 ppb; NMOR: 0.5 ppb in oil.)
After nitrosation by NOX in the laboratory, most of the oil samples
produced NDMA and NMOR indicating that the precursors for these nitrosamines
already exist in the oil and in fact NDMA and NMOR were the only two volatile
nitrosamines observed in the crankcase emissions. The nitrosation ability did
not show any correlation with the nitrogen content of the oil (see Appendix I
for nitrogen content of some oils).
The nitrosamine levels obtained by nitrosating certain unused oils can be
used to determine the susceptability to nitrosation of those oils in high
nitrogen oxide environments such as those found in the crankcases of automobiles
and trucks. A high positive correlation of r = 0.97, r^ = 0.94 (see Table 17)
between the two has been demonstrated for Mack ETAY B 673A engine. The
regression line is given in Figure 13. Therefore, for this engine, and under
the conditions we performed the testing, given the nitrosation level of a new
oil, the NDMA emission rate after one hour of preconditioning can be predicted
using the equation y = 8 + 0.3x, y being the NDMA in the emissions; X being the
nitrosation level of the new oil. It is unknown if this relationship is valid
after extended periods of engine operation.
-------
IV-9
Data from the light duty vehicle also show the presence of nitrosamines in
the crankcase emissions and high value of NDMA/NO.N02 ratio for this vehicle
agrees with the assumption that low crankcase flow rates will produce more
nitrosamines per unit NO.N02 (See Table 9).
Diesel tailpipe exhaust from a Mack Diesel engine was also collected and
analyzed for volatile nitrosamines. The pertinent results are given in
Appendix H.
-------
IV-10
Table 18
Linear Regression Results for NDMA versus NO.N02
Oil
r
r2
Mack
1
0.78
0.61
Mack
2
0.80
0.64
Mack
3
0.90
0.81
Mack
4
0.93
0.86
Caterpillar
4
0.72
0.52
Detroit
4
0
0
Diesel
.87
.76
Mack
Caterpillar
Detroit
Diesel
4
0.92
0.85
Table 19
Linear Regression Results for NMOR versus NO.NC>2
Oil
r
r2
Mack
1
-
-
Mack
2
-
-
Mack
3
0.85
0.72
Mack
4
0.97
0.94
Caterpillar
4
0.89
0.79
Detroit
4
-
-
Diesel
Oil 1 Shell Rotella T SAE 30
2 Amoco 300 SAE 30
3 Mobil Delvac 1200 SAE 30
4 Mobil Delvac Super 45 W 40
- NMOR was not detected
-------
A-l
Appendix A
Scope of Work
-------
JUL 3 1 1978 A-2
68-03-2719
A
Scope of Work
A. The major objective of this work is to qualify and employ a suitable
sampling and analysis methdoiogy in the testing of several heavy duty
diesel engines for crankcase emissions of nitrogen compounds such as
nitrosamines and n? trosamine precursors. The selection of test engines
should be such that a better estimate of the magnitude of the nitro-
samine (or precursor) emission problem can be made. In order to achieve
these objectives, the following tasks shall be performed.
B. Task 1 - Sampling and Analysis Methodology Qualification
1. There are several crankcase emissions sampling methodologies that have
been used in the past. Whereas one or mere of these methods may function
adequately, none of them have yet been well qualified. Therefore, the
contractor, with input from the OMSAPC and ORD Co-Project Officers,
shall select the most appropriate such crankcase emissions sampling
method, sec it up, and qualify its performance. This qualification
shall consist of, as a minimum, recovery and blank tests. . Recovery
tests are considered to be those that prove that if nitrcsamines or
their precursors are present in the blowby stream that they will indeed
be detected. The blank tests are those that confirm that artifact
nitrosamines (or precursors) are not being formed by the smapling or
sampling handling method. An example of such artifact nitrosamine for-
mation would be the possible formation of n-dimethylnitrosamine from
dimethylaminc and NOx , in an acidic environment. The major emphasis
in the qualification phase will be with n-dimethylnitrosamine and
n-diethylnitrosamines . The Project Officer shall approve of the
sampling method's performance prior to its use for engine testing.
2. The method used for analyzing the samples that result from both the
system qualification phase and engine testing shall have a detection
limit no higher than 30 parts per trillion (Vol/vol) . Structural
evidence of the nitrosamine compounds detected is also required, at
a detection limit of 30 parts per billion (Vol/vol) . The analytical'
services can be provided by the Contractor either directly or through
a subcontract. This task plus the GC-MS analyses required in Task III
should represent about one-half of the total contractual effort.
C. Task II - Engine Selection
The Environmental Protection Agency shall select and provide, or arrange
for the engines to be tested. A total of three (3) engines shall be tested
-------
A-3
SCOPE OF WORK
68-03-2719
D. Task. Ill - Engine Testing
The engines shall be operated over a 13 mode schedule. During chc 13
mode schedule, measurements will be made of at least NOx and total
gaseous blowby rate. Samples shall also be taken for subsequent
analysis by the methods described in Task I. The analyses should
concentrate' on nitrogen containing compounds such as nitrosamines
and their precursors. Structural evidence of any nitrosamines detected
must be provided. It is understood Engine Testing shall be accomplished
by an EPA designated source. The contractor will not do the testing
but shall take samples.
-------
Appendix B
Diesel Fuel Analysis for Nitrosamines
-------
B-2
Number 2 fuel oil was obtained from the fuel tank of Mack diesel 675.
30 ml of the fuel was extracted with 2 x 5ml 25% Methanol (MeOH) in water
(H20) in a separatory funnel. MeOH/t^O layer was poured into a Preptube™
and extracted with 50 ml DCM. DCM was reduced to 1 ml in 55°C waterbath and
analyzed on GC-TEA and HPLC-TEA. It showed 9 ppb NDMA on GC and 3 ppb NDMA on
HPLC. Whether this could be a likely source of nitrosamines in the crankcase
emissions has not been investigated.
-------
C-l
Appendix C
Engine Variable Measurements Provided by SWRI
-------
C-2
SOUTHWEST RESEARCH INSTITUTE
POST OFFICE DRAWER 28510 • 8220 CULEBRA ROAO - SAN ANTONIO. TEXAS 78284 . (5121684-5111
August 6, 1979
TO: Environmental Protection Agency
Ann Arbor, Michigan 48105
ATTN: Thomas M. Baines
Project Officer
RE: EPA Purchase Order A-0284-NALX
Dated June 1, 1979
i
SUBJECT: Final Letter Report "Diesel Engine Crankcase Samples
and Related Data."
From July 26 to August 3, 1979, several HD Diesel engines and
one light-duty Diesel vehicle were operated for the purpose of col-
lecting samples of the crankcase vent gases for DMNA analyses. The
sampling for DMNA was carried out by staff (Ulku Goff and Jim Coombs)
the New England Institute of Life Sciences while the supplemental
data of engine operation, NO, NOX and N02 content of the vent gases,
20 x 20 Pallflex filters (Mack engine only) and related items were
performed by SwRI. The engines and vehicle were those already at
SwRI having been used in previous EPA projects through the courtesy
of the respective manufacturers.
It is understood that the data will be used by NEILS in their
final report to EPA. Therefore, the data are appended in their most
available format. The limited nature of the purchase order precludes
any reformatting of already available data. Therefore the use of
Xerox copies is considered satisfactory.
In accord with the scope of work for the purchase order, the
following items are supplied:
A. HD Diesel Engines
1. Full description of engines
2. 13-mode FTP HC, CO, NOX, BSFC smoke
3. Standards for comparison
4. Crankcase flow rates - 7 modes
5- -NOj and NO concentrations in crankcase vent gases
6. Temperature of the water in/out, engine O!JL, and crankcase
vent gases at point of sample
SAN ANTONIO. HOUSTON. TEXAS. AND WASHINGTON. O.C
-------
C-3
A 20 x 20 size Pallflex filter was taken during the 1900 rpm,
50 percent rated load condition of the Mack engine. The filters have
been sealed and stored in the freezer awaiting your shipping instruc-
tions. Data for the four filters of the Mack are listed below.
1. Engine Description
The DDAD 6V-71N engine was tested in the 4 valve head confi-
guration with B-60E injectors set at 1.500 timing. These injectors,
though certified use in this type engine, were not entered into pro-
duction as LSN60 injectors were retained. This engine is described
on Table 1. It was furnished to SwRI by DDAD in late 1971 and is
assumed to be a 1971 model year engine.
Table 2 describes the Mack ETAY(B)673A and the Caterpillar
3406 engines. The Mack was the engine used in the 1000 hour "durability"
certification test and is considered a prototype 1975 engine. The
Caterpillar engine was the 125 hour "emissions" engine for 1975 EPA
certification and is considered a 1975 prototype. The Caterpillar 3406
engine was tested in its indirect injection configuration which features
a pre-chamber type combustion system.
2. 13-mode FTP and Federal Smoke
Attached as Tables 3, 4, and 5 are typical 13-mode FTP
(pre 1979 test procedure) and cycle weighted BSFC results. Listed
below are Federal Smoke results for each engine.
Opacity, % by EPA meter
a b c
DDAD 6V-71N 12.3 5.7 25.6
Mack ETAY(B)673A 11.5 11.3 22.5
Caterpillar 3406 11.9 5.4 28.6
3. Standards for Comparison
The only standard in effect for the DDAD 6V-71N engine was
the 1970-1973 smoke requirement (Federal Smoke Test) of an "a" factor
of 40 percent and "b" factor of 20 percent. For the two 1975 engines
(Mack and Caterpillar) the 1974 Federal limits were "a"-20, "b"-15
and "c"-50 percent opacity. The Federal gaseous emissions standards
for the two 1975 year Diesel engines were CO 40 grams/bhp-hr (53.6
gramsAw-hr) and HC + NO as NO2 16 grams/bhp-hr (21.4 gramsAw-hr).
California had separate standards for 1975 model years and they were
40.2 gramsAw~hr CO (30 grams/bhp-hr) and HC + NO as NO2 of 13.4 grams/
kw-hr (10 grc.ms/bhp-hr) .
-------
6-4
4. Crankcase Flow Rates
Table 6 lists the crankcase flow rates measured for the
three HD engines. Those were obtained by means of a thin-plate
orifice and vacuum source adjusted to give zero psig gage pressure,
i.e., source atmospheric, at the crankcase vent.
5. NO-N02 Concentrations
Table 7, 8 and 9 lists the modal concentrations of the NO
and NO for each of the seven modes tested.
6. Temperatures
Table 7-9 also lists the various oil, water and vent gas
temperatures requested.
7. 20 x 20 Size Filter Samples
Table 10 lists the filter weights for each of the four 20 x 20
size Pallflex filters taken of the Mack crankcase vent gases. The test
condition was the same for each oil, namely 1900 rpm and half load,
161.5 hp. Except for the first run which was curtailed due to an
electrical storm, each filter was run for 1 hour. The 20 x 20 filter
holder was located between an 8" diameter dilution tunnel and the CVS
blower and filtered the entire flow of diluted crankcase vent gases.
The nominal CVS blower rate was 85.7 CFM. The dilution level at the
1900/50 percent condition was about 15.2:1.
A practice run on 6/29/79 yielded 2.3574 grams of particulate
in a 1 hour test. The filter weights shown in Table 10 vary from 1.86
to 3.48 grams while sampling times varied from 3402 to 3600 seconds.
In terms of mg/SCF of flow across the filter, the third run, with
Mobil Delvac 1200, Filter PL 45, stands out as being high in weight
gain. This filter was reweighed to verify the increase. It was much
more oily than the other three runs. No other reason for the increased
weight was evident. This was discussed by telecon to Tom Baines on
8/2/79. For comparison, the practice filter has 0.459 mg/SCF on it.
8. Fuel Analyses
Table 11 lists the fuel inspection for the "National Averaqe"
No. ? fuel used in the> Mack and Caterpillar engines. This fuel was
EM-329-F and is a _rnmm.prH al rinl-f ?-p fne.1 witft sulfur content increased
to 0.235 percent bv weiqht. Table 12 lists the fuel inspection data
±or £M-4Uu-F the emissions type 1-D fuel used in the DDAD 6V-71N city
bus engine.
Prior to each HD test sequence, the engine was thoroughly precon-
ditioned by running for 30 minutes at intermediate speed and half load
and then for 30 minutes at rated speed and half load. Thus, each new
oil was run for 1 hour before testing began. A pint sample of used oil
was obtained at the conclusion of each test, tagged and furnished to NEILS.
-------
C-5
B. Light-Duty
In general, the same type of information was requested for the
1975 Mercedes-Benz 240D Diesel passenger car.
1. Vehicle Description
Table 13 describes the vehicle tested.
2. Tables 14 and 15 are typical 1975 FTP and HFET computer
printout sheets using the Emissions 2-D type Diesel fuel.
3. Emissions Standards
This being a 1975 model year car, the standards in effect
then were 1.5 g/mile HC (0.9 gAm) 15 g/mile CO (9.3 gAm) and
3.1 g/mile NOX (1.9 gAm).
4. Crankcase Vent Gas Rate
The crankcase vent rates for the 20 and 50 mph cruise (road
load set at 50 rnph) are listed on Table 16. Before taking this data,
the vehicle was operated for 30 minutes at 40 inph to bring oil and
other engine items to stabilized temperature. Shortly after measuring
the rates, the 20 mph cruise was run and sampled for 1 hour. The
sample at 50 mph was then run also for 1 hour.
5. NO-NO2 Content in Crankcase Vent Gas
Table 16 lists the NO and NO2 concentrations in the crankcase
vent gases.
6. Temperatures
Table 16 lists water in, out, oil and crankcase vent gas
temperature measured.
7. Fuel Analysis
Table 17 lists the inspection results for EM-321-F, the emis-
sions 2-D Diesel fuel used.
This completes EPA P.O. A-0284-NALX. As requested, a copy of this
report has been sent to Dr. David Fine at NEILS.
Prepared by:
Karl jy Springer
Direc/tZor
Department of Emissions Research
cc: Dr. David Fine
New England Institute for Life Sciences
125 Second Avenue
Walthawn, Mass 02154
-------
TABLE 1. DESCRIPTION OF HEAVY DUTY DIESEL ENGINE
Engine Make Detroit Diesel
Engine Model 6V-71*1)
Engine Serial No. 6VA53347
Strokes/cycle 2
Cylinder Arrangement V-6
Displacement liters 6.98
cubic inches 426
Compression Ratio 18.7:1
Type Aspiration Natural
Blower Scavenged
Rated Speed, rpm 2100
Power at Rated Speed, kW 163
hp 218
Peak Torque Speed, rpm 1200
Peak Torque, N-M 819
Ib-ft 604
Typical Application City Bus
Typical Fuel Type DF-1
B-60E injectors at 1.500 timing setting
TABLE 2. DESCRIPTION OF HEAVY-DUTY DIESEL ENGINES
Engine Make Mack Caterpillar
Engine Model ETAY(B)673A 3406 IDI
Engine Serial No. 6F4310 1A5484
Strokes/cycle 4 4
Cylinder Arrangement 1-6 1-6
Displacement, liters 11.01 14.63
cubic inches 672 893
Compression Ratio 14.99 16.5:1
Type Aspiration TC(a) TC^a)
Rated Speed, rpm 1900 2100
Power at rated speed, kW 235 242
hp 315 325
Peak Torque Speed, rpm 1450 1400
Peak Torque, N-M 1423.8 1319
Ib-ft 1050 970
Typical Application IC^ ic(b)
Typical Fuel Type DF-2 DF-2
(a) TC-Turbocharged, NA - Naturally Aspirated
(b) IC-Intercity Truck, Tractor, U - Urban Truck and Truck-Tractor
-------
C-7
TABLE 3. 13-W00£ FEDERAL OUSEL EMISSION CYCLE
DD-AO bV-71 N COACH ENGIME wITH B-bCE IMJECTOR3 1,500 TIMING
TEST i RUN X 3-24-75 1-0 FUEL EM-22b-F PROJECT! ll-401b-001
MOD?: ENGINE TORQUE
SPEED
RPv N X M
1
2
3
4
5
b
7
e
s
10
11
12
13
MODE
1
e
3
4
5
b
7
8
S
10
11
12
13
CYCLE
440
12bO
12hO
12bO
I2fa0
12hG
4 ')0
2100
2100
2100
2100
2100
4<;0
HC
PPM
88
Ib8
lib
79,
84
IbC
152
IbS
112
89
88
23h
188
COMPOSI
2.
2,
185,
375,
557.
740,
2,
b22 ,
470,
311,
Ibl,
2 ,
2»
CO*
PPM
107
254
158
78
90
1348
lOb
373
lib
85
105
193
133
TE
V
4
2
1
9
7
4
0
0
0
*
4
4
KW
.1
,3
24 , 4
41,5
73, b
97.7
.1
13b.8
103,4
bB.4
35,5
, 5
,1
N0t +
PPM
124
b2
188
355
b4q
9HB
124
780
b2&
280
150
58
128
BSHC
BSCO*
BSN02+-*
es
HC *
B
SN02-H-
R FUEL
FLOw
KG/MJN
.023
Ob3
123
203
283
393
023
55H
4WI,
334
238
151
023
WEIGHTED
Kh
• 01
,03
1.95
3. 9b
5,89
7,82
.01
10,94
8,27
5,4?
2,84
,04
.01
= 1.238
= 4 ,bOb
= ll,5bl
= 12,799
AIR
FLOW
KG/MIN
4,5b
IS^b
13. b4
13,55
13,13
13,34
4,53
21.75
21, bl
21,35
21,42
21.75
4,53
BSHC
G/KW HR
107,20
207,97
1,90
, b4
,45
,bS
183,95
,80
.70
.82
l,5b
283,21
227,51
GHAM/K*
GRAt-VKrt
GRAM/KW
GRAM/KW
KG/
H%
13%,
13,
13,
13,
13,
22!
22,
21.
21.
21,
*,
^[N
rg
32
7b
75
41
73
55
31
Ob
b8
bb
91
55
ft 1 P.
RATI
,005
,005
,009
,015
,022
,029
,005
,02b
,021
,01b
,011
,007
,005
0
BSCO* B5^02t-f
G/R
258
b25
5
1
10
25b
3
1
1
3
470
320
HR
HH
HR
HR
rt HR
,5b
,58
,18
,2b
, 95
,93
.71*
,53
.43
,5b
.72
. ^9
.77
G/K'r,
495,
249 ,
10,
ll!
4S1,
12.
10,
8,
8,
230,
507,
HR
75
53
10
39
27
22
2b
12
74
47
74
93
b?
HUM,
MILLI
G/KG
2,1
2,1
2,1
2,4
f
2)4
2)4
2,4
2,*
2,7
2.7
t '
BSFC
^CONVERTED TO ^ET BASIS
^ CONVERTED TO .':ET BASIS AND CORRECTED TO 10.7 MILLIGRAMS
HATE/? Ph3 KG DRY AIR
-------
TABLE 4.
OirSKl M1TMON CYCLR
PHiJt.CT : I.
EriGTur- : '
HOOF. (• MR I '.'r.
i bsn
3 ) "»5M
V j Y t; p |
5 1 1 50
h 1 H Sll
7 b^n
8 j'liin
H 1'liM)
in , tlil'i
11 l'U"i
I? lli'll
Ij l.S'l
I -Vt?rf-IIM J WAIfc 1-H-7H
IIM:K ti AYf f<)-K7?A wiiiioiu
TURf.'Uc
\J X ft
",n
3 is. 5
HRb. 1
li't b.i
13H.1
u. it
U?s.j
3 'Hi.?
bl'S. 3
•M'b. ?
13. ?
ll.li
TEST NO. 1
HJf) APf I'ljMP
fl'^'E" Fl't-'L Air'
FLOW FLOrf
n.u
51 .5
HIM .a
15H.M
s n . r.
n.u
C37!. f
1 7 J. 1
J ? n . H
h '! . ')
b.h
n. n
."I? *
.O;H o
.? 1 b J II
.3HS J 3
.^71 17
.771 pi
.D17 3
.yi'7 87
.(••TO ?3
. f ?S 1 1
! ? 7 1 J «.
.Jl 7 J?
.11.17 3
:"
. 7h
.an
.en
.ru
.Ri
.f-7
,<;f.
• •* b
.(.()
.R?
.1H
EXHAUST FIJK.L
F L f 1 H_ AIP
KR/MIH KAFIO
3.Hh ,'iij';
111.18 .ll?tl
. 1 •» . P. ?. .UfS
17. PS .033
HI. 78 .H37
3.1] .IMl'f
as.bn .1133
?f.?t .1121
.?n.(j3 .DPI
j <; . R 3 . o i R
IP.IH .nni
3.1h .HOM
MODE
I
a
3
t
1
b
7
>j
H
in
11
12
13
CYCLE
HC
PPM
ah?3
•tin
2bH
m
an
DSHC =
BSCO-f =
BSNO?++=
BSN02+t=
WEIGHTED
KW
n.uo
.37
H . ia
8.33
ia.?e
IH.Htl
o.oo
1". 7o
It. 17
H.b3
H.87
.53
n.uo
. 707
i.iat
9.87S
in.ssa
BSHC
Q f f\ vi Ho
R
IS. 11
1.H3
.71
.31
.1"
K
.23
.H-5
.S5
1. 5b
it. q?
R
GRAM/KW
GRAM/KW
GRAM/KW
GRAM/KW
8SCU +
G/KW HR
R
a?. in
l.bl
1.U2
l."» 7
2.03
H
l.«3
1.37
1.1*
2. e!b
20. H5
R
HH
HH
HR
KR
BSN02t+
G/KW HR
R
17.1*
10.18
11. SH
11.35
10.81
R
8. Ha
8.13
b. 17
b.5»
2b. 31*
R
HUM.
MILLI
G/KC
f .4
H.*
* .*
*.*
*.*
* .*
*.*
*.*
*.*
*.*
* . *
* .*
V , H
8SFC
.g'UKG/KW HR
CONVERTED TO WET BASIS
CONVERTED TO WFT BASIS AND CORRECTED TO 10.7 MILLIGRAMS
WATER PER KG DRY AIR
n
I
oo
-------
TABLE 5. 13-MOOE FEDERAL DIESEL EMISSION CYCLE
PROJECT: u-nz3-ooi TEST DATE *-ie-7B TEST NO.I
CATERPILLAR 3*ob INDIRECT INJECTION FUEL EK-
"ODE
1
2
3
*
5
b
7
9
1
10
11
12
13
ENGINE
SPEED
RPH
bOO
1*00
1*00
1*00
1*00
1*00
bOO
2100
2100
2100
2100
2100
bOO
TORQUE
N X M
0.0
2b . 1
33*. 7
bS7.1
1001.8
13*3. b
0.0
1113.*
8*0.'*
SbO.2
280.1
H.O
0.0
POKER
KW
c.o
3.8
*S.l
17.8
l*b. 4
117.0
0.0
c** . 8
18*. 8
123.2
bl.b
*.2
0.0
FUEL
FLO*
KG/KIN
.02b
,ai7
,228
. 331
.53b
. 8QR
, 02b
1.037
.777
.5*1
.337
.177
.031
AIR
FLOW
KG/MIN
*.23
10.00
10, 3b
11.11
l*.bb
17.28
*.7b
2*. VI
20. b2
lb.75
l*.bS
13.83
*.7b
EXHAUST
FLOW
KG/MIN
*.2b
10.10
10.51
12.30
15.25
18.01
*.71
25.**
21. *0
17.21
1* . 11
1*,01
*,71
FUEL
AIR
RATIO
.OOb
.010
.022
.033
.0*0
.0*7
.005
.0*2
.038
.032
.023
.013
.007
MODE HC
PPM
1
a
3
*
5
b
7
8
q
10
11
12
13
CYCLE
120
1*8
Sb
28
12
b
b3
2*
*0
12
28
bO
1b
CO +
PPM
*11
*b*
173
11*
IS*
377
*1b
Ibb
1*0
85
lib
212
382
COMPOSITE
BSHC +
NO++ WEIGHTED
PPM KH
b3
b3
*3S
517
582
b2b
83
735
bll
517
*23
118
*5
BSHC a
BSCO+ =
BSN02t*3
6SN02 + + =
0.00
.31
3.13
7.82
11.75
15.7b
0.00
11.51
1*.78
1.8b
*,13
,33
0.00
.17b
1.131
b.150
7.12b
BSHC
G/KW HR
R
11. 3S
.35
.10
.0*
.02
H
.07
.13
.05
.20
S.8b
R
G3AM/KH
GRAM/KW
GRAM/KW
GRAM/KH
SSCO +
<",/KH HR
70
2
1
2
1
1
5b
HR
HR
HR
HR
R
• 1b
.17
.83
.17
.01
R
.00
.1*
.bl
.b*
.82
R
BSSOc+t
G/KK HR
15
8
b
5
5
7
b
b
1
37
3
.73
ill
.75
. * 7
H
.27
.7*
."I
,80
.80
R
HUH.
M1LLI
G/KG
b.2
b . 2
b.2
b.2
b.2
b.h
b . b
b.b
b.7
b.*
b.*
b.*
b. *
B3FC
.272KG/KH HK
CONVERTED TO HET BASIS
CONVERTED TO WET BASIS AND CORRECTED TO 10.7 MILLIGRAMS
WATER PER KG DRY AIR
n
VD
-------
TABLE 6. ENGINE CRANKCASE VENT SATES
C-10
Test Mode
Speed
Load, %
Intermediate
50
100
Idle
100
Rated
50
DDAD 6V-7IN
Speed, rpm
Power, hp obs
Flow, Ibs/hr
SCFM
m3/min
m3/30 min
1260
3.8
4.01
0.89
0.02
0.6
1260
66.4
3.90
0.87
0.02
0.6
1260
132.7
4.03
0.90
0.02
0.6
400
1.61
0.36
0.01
0.3
2100
190.4
10.42
2.32
0.15
4.5
2100
95.2
9.31
2.07
0.06
1.8
2100
3.5
8.04
1.79
0.05
1.5
Mack ETAY (B)673A
Speed, rpm
Power, hp obs
Flow, Ibs/hr
SCFM
m^/min
m3/30 min
1450
6.3
10 ..71
2.38
0.07
2.1
1450
139.7
19.5
4.34
0.12
3.6
1450
283.2
31.8
7.08
0.20
6.0
600
7.66
1.70
0.05
1.50
1900
313.5
43.77
9.74
0.28
8.4
1900
161.5
25.35
5.63
0.16
4.8
1900
8.9
12.9
2.87
0.08
2.4
Caterpillar 3406 IDI
Speed, rpn
Power, hp obs
Flow, Ibs/hr
SCFM
m~/min
m3/30 min
1400
5.1
13-10
2,91
0.082
2.5
1400
133.9
19.10
4.25
0.12
3.6
1400
268.3
30.89
6.87
0.19
5.8
600
14.91
3.32
0.09
2.7
2100
327.6
29.44
6.55
0.18
5.4
2100
163.8
24.12
5.37
0.15
4.5
2100
7.0
18.48
4.11
0.12
3.6
-------
TABLE 7. ENGINE TEMPERATURES AND CRANKCASE GAS NO-NO2 READINGS
Mack ETAY(B)673A
C-ll
Test Mode
Speed
Load, %
Speed RPM
Power, hp ohs
Temps °F oil
water in
water out
crankcase
NO,ppm
NO.-, pprn
Temps °F oi1
water in
water out
crankcase
NO, ppm
NO2, ppm
Temps °F oil
water in
water out
crankcase
NO, ppm
NO
2'
ppm
Temps °F oil
water in
water out
crankcase
NO, ppm
NO9, ppm
1
2
3
Intermediate
2
1450
6.
50
1450
3 139.7
100
1450
283.
Shell Rotella T
186
180
181
162
22.
3.
185
181
181
161
25.
4.
185
178
180
161
22.
9.
185
178
179
161
23.
3.
198
174
178
180
5 75.3
0 69.3
Amoco 300 30
196
178
181
180
3 101.4
1 69.9
Mobil Delvac
195
173
181
177
5 105.3
7 69.9
Mobil Delvac
195
173
182
178
3 90.3
3 59.4
208
172
183
219
114.
74.
wt
206
178
182
212
132.
88.
1200
206
175
182
210
114.
64.
Supe
208
171
183
212
144.
91.
4
Idle
-
600
2
5
100
1900
313.
30 wt Em-296-EO,
174
179
179
172
6 17.1
1 4.0
EM- 39 2 -EO- A,
171
179
180
154
6 13.8
8 1.9
215
173
184
226
127.
109.
6
Rated
50
1900
5 161.5
7/26/79
201
174
182
198
5 100 . 2
8 33.6
7/27/79
213
175
185
224
123.
86.
30 wt EM-M8-EO/
173
180
180
169
0 20.5
8 3.7
213
173
184
223
123.
97.
r 15W40 EM-399-EO,
175
179
180
173
6 21.6
5 4.5
214
172
183
220
128.
117.
200
174
183
191
3 69.6
7 72.6
7/3&/T9
201
174
182
195
3 84.0
2 54.6
7/31/79
203
178
181
197
1 101.7
9 41.1
2
1900
8.9
190
179
178
165^
33.4
6.1
188
177
178
161
31.0
7.5
189
174
176
165
29.4
6.2
189
174
179
165
26.4
10.3
-------
C-12
TABLE 8.
Test Mode
Speed
Load, %
Speed, rpm
Power, hp ohs
Temps °F oil
water in
water out
crankcase
NO, ppm
ENGINE TEMPERATURES AND CRANKCASE GAS NO-NO2 READINGS
Detroit Diesel 6V-71N B60E
Mobile Delvac Super 15W40, EM-399-EO 8/1/79
2
1260
3.8
183
165
172
155
2.4
1.3
Intermediate
50
1260
66.4
196
164
177
160
4,3
0.4
100
1260
132.7
216
186
166
171
11-. 4
1.0
4
Idle
400
177
169
172
143
7.3
0.5
5
100
2100
190.4
216
166
184
190
19.3
1.0
6
Rated
50
2100
95.2
204
166
178
183
5.5
0.9
7
2
2100
3
196
166
175
178
1
0
.5
.7
.7
TABLE 9.
Test Mode
Speed
Load, %
Speed, rpm
Power, hp ohs
Temps "P oil
water in
water out
crankcase
NO, ppm
NO, ppm
ENGINE TEMPERATURES AND CRANKCASE GAS N0-N02 READINGS
Caterpillar 3406 IDI PC
Mobil Delvac Super 15W40, EM-399-EO 8/2/79
2
1400
5.1
183
161
169
152
6.9
0.4
Intermediate
50
1400
133.9
197
162
178
173
24,5
2.1
100
1400
268.3
215
164
192
217
20.6
4.3
4
Idle
600
174
161
168
163
4.2
0.4
5
100
2100
327.6
225
164
190
227
54.9
9.3
6
Rated
50
2100
163.8
212
163
179
198
35.4
3.3
7
2
2100
7
200
162
172
168
37
0
.0
.0
-------
C-13
TABLE 10. 20 x 20 Filter Data - MACK ETAY(B)673A
Oil Code EM-
Oil Description
SAE Wgt.
Filter Number (SwRI)
EPA Filter Code CABS-79-
Filter V7eight, grams
Sample Time, sec
Diluted flow across
filter, SCF
Rate, mg/SCF
396-EO
Shell
Rotella T
30
PL- 4 3
0240
1.8593
3402
4732
0.393
397-EO-A
Amoco 300
30
PL-44
0250
2.2231
3600
5072
0.438
398-EO
Mobil Del vac
1200
30
PL- 4 5
0260
3.4825
3600
5106
0.682
399-EO
Mobil Delv
Super
15W40
PL-47
0270
2.3427
3600
5073
0.462
-------
C-14
TABLE 11. GULF NO. 2 ANALYSIS
MEMORANDUM
TO: Bob Scubar
FROM: Rick Thieson - 08
SUBJECT: REPORT OF ANALYSIS ON EM-329-F, TANK 15 & 17
GULF #2
A. P. I Gravity - 37.0
Viscosity @ 100°F - 2.50 cs
Sulfur, wt % - before treatment 0.108
after treatment 0.235
Cetane No. - 50.2
Distillation °F IBP - 328
10 - 411
50 - 499
90 - 578
EP - 641
% Rec - 98.5
% Res - 1.30
% Loss - 0.20
F. I. A. %
Aromatics - 23.0
Olefins - 1.14
Saturates - 75.82
Flash Point °F - 155
Their values seem to match with the typical values supplied, and
the before/after sulfur wt % seems to be as expected.
Billing should come to you at a later date.
If I can help on anything else, please let me know at 2868.
RT/djb
-------
TABLE 12. EMISSIONS 1-D
C-15
nUVYJtLL n I UKUCAKtiVJPO -
San Antonio, Texas '•>
LABORATORY REPORT />/* /e No. I- -2
+ ml TEL
fotjl Sulfur,
\Vl.%
Mercaptan Sulfur
I lash, F.
Pour Point, F.
Cloud Point, F.
Freeze Point, F.
Smoke Point, mm
AnUine Point, -F.
Aniline Gravity
Const.
Water Tolerance
42.9
.18
+ 140°
Date
6-19-79
DISTILLATION
Diesel Index
Cctanc No.
Viscosity, S S
& F
Viscosity,
B.S.&W.
A.S.T.M.
Existient
Gum, mg.
PotentiaJ
Gum, mg.
%@
%@
%@
%@
%@
%@
%@
49.0
1.7
[nitiaJ
Boiling Point
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
End Point
Recovery
Residue
Loss
Paraffins,%
Olefins.%
Naphthenes, %
Aromatics,%
374
392 !
398
404
408
414
418
422
429
440
461
496
560
99.0
1.0
[
16.2
'
Remarks:
Tested By:
Tuu S. McLeod, Chief Chemist
-------
C-16
TABLE 13. DESCRIPTION OF TEST VEHICLES
Vehicle Model
Engine Model (if different)
Mercedes 240D
OM616
V.I.W.
Engine No. (if different)
Body Type
Loaded Weight, kg (Ib )
Inertia Equivalent, kg (Ibr)
m
Transmission
Displacement, &(in )
Cylinders
Power, kW (hp) @ rpm
Injection System
Combustion Chamber •.
Compression Ratio
Distance on Vehicle, km
11511710066208
616916-10-052895
4 door sedan
1492 (3289)
1588 (3500)
4 speed manual
2.40 (146.7)
4
46.2 (62) @ 4350
Bosch
prechamber
21.0
7182
curb weight plus 136 kg (300
at end of project
-------
UNIT NO. ; ; ;
VEHICLE: MOOTL
TEST TYPE 5Y
TEST wo. 5
MEKCEOES DIESEL
BAROMETER 74S.2a MM OF HG.
DRY BUL8 TEMP. 23.9 OEG.
REL. HUMIDITY 44 PCT.
EXHAUST EMISSIONS
PLQWER DIF. PRESS., G2,
TAHLC 1.1 VEfJlCLf! EMISSION «E3ULTX
LIGHT DUTY CMIUOIONS TEST
DATE 3/lb/77
ENGINE a.41 LITRE b CYL.
COMMENTS 1975 FTP 3 BAG EM-238-F
MFGR. CODE -0
TEST KT. 1S87 KG
Y U . 19 7 <;
HOAO LOAD
H,4 KW
MM. nao
WET BULB TEMP lb.1 OEG. C
AHS. HUMIDITY B.3 MILLIGRAMS/KG
R INLET PRESS., Gi 40b.4 MM. H20
13LOWER INLET TEMP. * 3 DEC. C
(JAG RESULTS
BAG NO.
BLOWER REVOLUTIONS
HC SAMPLE METER READING/SCALE
HC SAMPLE PPM
HC OACKGRO METER READING/SCALE
HC BACKGRD PPM
CO SAMPLE METER READING/SCALE
CO SAMPLE PPM
CO BACKGRD METER READING/SCALE
CO BACKGRD PPM
C02 SAMPLE METER READING/SCALE
C02 SAMPLE PERCENT
COe BACKGKD METER READING/SCALE
COa BACKGRD PERCENT
NOX SAMPLE METER READING/SCALE
NOX SAMPLE PPM
MOX BACKGRD METER READING/SCALE
NOX 3ACKGRD PPM
HC CONCENTRATION PPM
CO CONCENTRATION PPM
C02 CONCENTRATION PCT
NOX CONCENTRATION PPM
HC MASS GRAMS
CO MASS GRAMS
CO? MASS GRAMS 13
NOX MASS GRAMS
HC MASS HG
WEIGHTED MASS HC ,ia GRAMS/KILOMETRE
WE1GHTF.D MASS C.O .57 GRAMS/KILOMETRE
WEIGHTED MASS CO,? 224.9V GH AMS/K I LOME TRF
WEIGHT F.D MASS NOX .79 GO A MS/K I LO'"ET KF.
I
9129
4.8/4
39
b.2/2
ia
4b . 9/»
- 44
1.2/*
1
ba.9/3
1.12
3.1/3
.05
37. i/a
37.1
.b/2
.b
27
42
i.ns
3b.b
1.08
3.34
bS.39
4.48
1.08
a
ISbl?
21
5.8/2
18
32. b/*
30
1 .?/*
a
f a.b/3
.73
H.3/3
.07
as. 1/2
25.1
.b/2
.b
13
28
.bb
2H.S
.87
3.87
141H.83
5.17
.87
aa
b.a/a
12
31. a/*
37
i.a/*
i
SS.b/3
35.0/2
35.0
.b/a
.b
11
31.4
.45
2.7b
4.a
CARBON BALANCE FUEL CONSUMPTION : 8.42 LITRES PER HUNDRED KILOMETRES
TOTAL CVS FLOW = 2Sb.9 STD. CU. METRES
I
I—"
^J
-------
TABLE 15.
EXHAUST. EMISSIONS FROM SINGLE BAG SAMPLE
VEHICLE NUMBER
-0 HRS.
PATE 3/lb/77 TIME
KODEL 1*75 MERCEDES DIES. FET
DRIVER DT TEST WT. 1587 KG.
WET P'JLB TEMP 17 C DRY BULB TEMP 2» C
SPFC. HUM. 8.8 GRAM/KG 8ARO. 74S.7 MM HG.
DISTANCE Ib.t7b KM FUEL 8
-------
C-19
TABLE 16. MERCEDES-BENZ 240D CRANKCASE DATA
Mobil DELVAC SUPER 15W40, 8/3/79
Vehicle speed, raph 20 50
Vehicle HP, indicated T74 1TT9
actual 11.2
Flow, Ibs/hr 3.85 5.35
SCFM 0.86 1.19
ra3/min. 0.025 0.035
m3/30 rain. 0.75 1.04
Temps. °F oil 189 234
water in 87 169
water out 173 187
crankcase 121 151
NO, ppm 6.2 8.0
N02, ppm 0.4 0.6
Inertia - 3500 Ibs
1 Ib/hr = 0.0065 m3/min.
-------
TABLE 17. EMISSIONS 2-D Fuel
MEMORANDUM
C-20
TO: All who use Emissions 2D fuel
FROM: Karl J. Springer^' '
DATE: March 20, 1978
The latest batch of Howell 2D Diesel Emissions fuel is coded EM-321-F
and is in Tanks 5 & 6. The inspection data is shown below. This fuel is
in use effective on its delivery of about 3/15/78.
cc:C. T. Hare
O. %7. Davis
S. F. Martin
T. L. Illman
J. G. Chessher
V. Markworth
R. Hull
o'
I1
cr
O
o
O
rr
PJ
Wulct Toll
I
i S
e 1
P....
C o
H ^;-
V*
Aniline Gi
Const.
<
~ i
ifS
w — r~
3
5'
n
1
4j
l
c:
w
£
1
0
2.
3"
f i
H
1 ?
I
.•"5
to
.£,.
o
o
o'
••^
O
Ul
0
t*
-3
O
£
*?; '
0
— o
^
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,5,
•^-
o
i;
?
fl
*
o
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c
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,**
SJ
o
CJ
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r>
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ij
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S.
a"
o
X
t>
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Octane N
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ri '"
vr>
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t*
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p
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r>
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-------
D-l
Appendix D
Comparison of GC-TEA and GC-MS Results
-------
D-2
Confirmation of NDMA on GC-TEA and GC-MS.
GC-TEA GC-M
Sample No. Engine Oil (ppm) (ppnO
1 Mack ETAY (B) 673A Mobil Delvac Super 15 W 40 5.1 5
2 Mack ETAY (B) 673A Mobil Delvac 1200 4.9 5
3 Caterpillar 3406 Mobil Delvac Super 15 W 40 1.9 2
4 DDAD 6V-71N Mobil Delvac Super 15 W 40 1.6 1
5 Mack ETAY (B) 673A Amoco 300 SAE30 1.4 1.5
-------
LABORATORY OF THE GOVERNMENT CHEMIST 0-3
Cornwall House, Stamford Street, LONDON S.E.1
Telephone: 01-928 7900, ext. 625
Phase address any reply to
THE GOVERNMENT CHEMIST 14 December 1979
and quote:
Your reference:
Dear Dr. Goff,
With reference to your letter of 1 3 November 1979* I am sorry that I have
been so long in replying however" I list belo^ the information that you require :-
Results of analysis by GC-high resolution MS:-
Sample 1 NDMA 5 ppm
Sample 2 NDMA 5 ppm
Sample 3 NDMA 2 ppm
Sample 4 NDMA 1 ppm
Sample 5 NDMA 1.5 ppm
The instruments used were a Kratos-AEI MS902 mass spectrometer operated in
the peak matching mode and coupled to a Pye 104 gas chromatograph using a silicone
rubber membrane separator.
The conditions of analysis were as follows:-
Gas Chromatograph:-
Carrier gas Helium
Flow rate 15 ml/min
Temperatures Injection port 170 C
Column 160°C
Separator 160 C
Transfer line 160°C
Column 10 ft x 1/8 inch stainless steel, 5% Carbowax 20M on 80-100 BS
mesh acid washed Chromosorb W.
Sample size
-------
D-4
Mass Spectrometer:-
Accelerating voltage 8 kV
Trap current 100^iA
Electron beam voltage (El mode) 60 eV (tuned for maximum monitor response )
Multiplier voltage -2.8 kV
-6
Ion source pressure 3 x 10 torr
Resolution (10% valley) 7000
A fuller discussion of this type of procedure is given in J. Chromatogr. 64*
201-210 (1972) by T A Gough and K S Webb.
If any of these points require further clarification please do not hesitate
to contact me.
Yours faithfully,
-------
D-5
Figure Captions:
Figure 14 GC-TEA analysis of the combined extracts that were con-
firmed on GC-MS.
Figure 14-a 4 ng NDMA standard
Figure 14-b Sample 1, showing the presence of 5.1 ppm NDMA in
solut ion.
Figure 14-c Sample 2, showing the presence of 4.9 ppm NDMA in
solution.
Figure 14-d Sample 3, showing the presence of 1.9 ppm NDMA in
solution.
Figure 14-e Sample 4, showing the presence of 1.6 ppm NDMA in
solution.
Figure 14-f Sample 5, showing the presence of 1.4 ppm NDMA in
solution.
-------
D-6
(c) .
NDMA
J
(f)
NOMA
1 1 '
(b)
NOMA
(e)
NOMA
i I 1
\
1
(a)
NDMA
(d)
NOMA
L 1
J
1
1
86420 86420 86420
TIME (MINUTES) TIME (MINUTES) TIME (MINUTES)
Figure: 14
-------
E-l
Appendix E
The Information Supplied by Various Engine Manufacturing and Oil Companies
-------
Volume 63
Number 2
Lubrication
A Technical Publication Devoted to
the Selection and Use of Lubricants
PUBLISHED BY
TEXACO INC.
TEXACO PETROLEUM PRODUCTS
-------
E-3
LUBRICATION
A TECHNICAL PUBLICATION DEVOTED TO THE SELECTION AND USE OF LUBRICANTS
Published by
Texaco Inc., 135 East 42nd Street, New York, N. Y. 10017
Maurice F. Granville, Chairman of the Board
John K. McKinley, President; C. B. Davidson, Secretary; R. G. Brinkman, Treasurer.
Volume 63
Number 2
1977
COPYRIGHTS: The contents of LUBRICATION are copyrighted and cannot be reprinted legally by other publications without written prior
approval from Texacc and then only ij the article is quoted exactly and accompanied by the credit line "Courtesy of Texaco's magazine
LUBRICATION". Copyright © 1977 by Texaco lac. Copyright under International Copyright Convention. All rights reserved under Pan
American Copyright Convention.
CHANGE OF ADDRESS' In reporting change of address please give both old and new address: Write to—A. H. Lou-man, Texaco Inc',
2100 Hunters Point Avenue, Long Island City, N.Y. 11101; or D. E. Presley, Texaco Canada Limited, 90 VynforJ Drive, Don Mills,
Ontario MIC 1K5 Canada.
R. F. Meeker. Editor
FUEL AND LUBRICANT ADDITTVES-II
LUBRICANT ADDITIVES
George J. Schilling and Gordon S. Bright
THE previous issue of this publication16 pre-
sented the function of and cited examples of
typical chemical additives commonly used in
gasoline, and in middle distillate and residual fuels.
This issue concludes the article with a general dis-
cussion of lubricant additives, and then presents a
detailed description of the additives typical of those
used in automotive drive-train and industrial lu-
bricants.
As emphasized in the previous issue, additives
cited in this arf'cle are examples only. Their men-
tion in this context is exemplary and illustrative,
and is not intended to imply that any particular ad-
ditive or additive package is used in any specific
commercial automotive or industrial lubricant, and
should not be inferred.
The term "additive" is used in this issue to cover
those materials added to a lubricant to impart or
enhance desirable properties^ or to eliminate or min-
imize deleterious properties. A lubricant can be
denned as a gas, liquid, or solid capable of reducing
friction, heat, and wear when introduced between
two solid surfaces in relative motion. Mineral oils
refined from crude oil provided satisfactory liquid
lubricants for machinery for many years, but most
modern equipment demands more from a lubricant
than mineral oils alone can provide. A variety of
additives has been developed to improve the proper-
ties of mineral oils, and to give them desirable new
properties. The trend to higher operating temper-
atures in automotive drive-trains, the imposition of
engine emission controls, and optimum industrial
production are reasons for the development of better
lubricants and a steady increase in additive produc-
tion17, as indicated by Figure 16.
Lubricant additives can be grouped into three
main functional areas: those which protect the lu-
bricated surfaces, those which improve lubricant
performance, and those which protect the lubricant
itself.18 The rslationship between additive types and
their functions is general, and can be applied to
lubricants for engines, transmissions and rear axles
in automobiles, trucks, off-highway equipment, and
a wide variety of industrial equipment. The formu-
lation of a lubricant for a specific application is a
difficult task which requires identification of per-
formance needs, knowledge of the additives that
meet those needs, and finally, careful selection of the
appropriate base oils and additives.
Many types of additives perform more than one
function. For example, zinc dithiophosphates protect
metal surfaces from wear and corrosion. They also
protect the lubricant from decomposition by pre-
venting the oxidation processes that lead to the
formation of corrosive acids and deposit precursors.
Thus, in this instance, the additive is multifunc-
tional.
One very important point must be made. In
C13]
-------
E-4
LUBRICATION
1.000
-------
E-5
LUBRICATION
TABLE I
SURFACE PROTECTIVE ADDITIVES
AUTOMOTIVE LUBRICANTS
Additive Type Purpose
Antiwear and
EP Agent
Corrosion and
Rust Inhibitor
Detergent
Dispersant
Friction
Modifier
Reduce friction and
wear and prevent
scoring and seizure
Prevent corrosion and
rusting of metal parts
in contact with the
lubricant
Keep surfaces free of
deposits
Keep insoluble con-
taminants dispersed
in the lubricant
Alter coefficient of
friction
Typical Compounds
Zinc dithiophosphates, or-
ganic phosphates, and acid
phosphates, organic sulfur
and chlorine compounds,
sulfurized fats, sulfides and
disulfides
Zinc dithiophosphates,
metal phenolates, basic
metal sulfonates, fatty
acids and amines
Metallo-organic compounds
of barium, calcium and
magnesium phenolates,
phosphates and sulfonates
Polymeric alkylthiophos-
phonates and alkylsuccini-
mides
Organic fatty acids and
amines, lard oil, high molec-
ular weight organic phos-
phorus and phosphoric acid
esters
Functions
Chemical reaction with metal
surface to form a film with lower
shear strength than the metal,
thereby preventing metal-to-metal
contact
Preferential adsorption of polar
constituent on metal surface to
provide a protective film and/or
neutralization of corrosive acids
Chemical reaction with sludge and
varnish precursors to neutralize
them and keep them soluble
Contaminants are bonded by polar
attraction to dispersant molecules,
prevented from agglomerating
and kept in suspension due to
solubility of dispersant
Preferential adsorption of
surface-active materials
faces in engines, and between gears in transmissions
and rear axles. In these areas, wear may appear as a
gradual polishing of the metal surfaces, or as scuffing
or spalling22. The right hand portion of Figure 17
illustrates severe wear on a valve lifter. Zinc dithio-
phosphates have enjoyed wide acceptance as anti-
wear additives in automotive lubricants.
Severe boundary lubrication conditions can devel-
op between the gear teeth in hypoid gear sets, and
the gears in the transmissions and axles of heavy
equipment23. Additives such as alkylpolysulfides,
tricresylphosphute or chlorinated organic com-
pounds are used under these conditions and are
referred to as EP additives.
Both antiwear and EP additives prevent metal-to-
metal contact between parts by forming a coating
that will yield under the shear stress imposed during
boundary lubrication20. Heat from friction between
mating surfaces provides energy for the chemical re-
action between the additive and metal surfaces that
results in the protective coating. Some additives re-
quire more energy to react than others, and unless
sufficient energy is available, the coating cannot
form. The costing may be an iron sulfide, iron
phosphate, or some other metallo-organic com-
pound, depending on the particular metal and addi-
tive present.
Corrosion and Rust Inhibitors
Corrosion is a chemical attack on metal surfaces,
and rust is a specific type of corrosion involving
ferrous metals. Corrosive materials contaminate
drive-train lubricants in a variety of ways. Lubricants
may oxidize in service to form organic acids. The
process of combustion introduces moisture and a
variety of organic and mineral acids into engine
crankcase oils10'24. Transmissions and gear cases
may ingest moisture from the atmosphere through
their vents as they cool after shutdown. Moisture
contamination can also react with some EP addi-
tives, hydrolyzing them to form acids. The chemi-
cally reactive nature of some EP additives can also
make them corrosive.
The additives used to prevent corrosion in auto-
motive equipment contain polar functional groups
that permit them to preferentially adsorb on metal
surfaces. This provides a barrier to prevent corro-
sive materials from contacting the metallic surfaces.
Zinc dithiophosphates and dithiocarbamates are
commonly used to protect copper-lead bearings
from the type of corrosion illustrated in Figure
18. Rust inhibitors derived from sulfonates and
amines also form adsorbed films on ferrous metals.
Careful selection of the components in a molecule
designed for inhibiting corrosion permits a tightly-
packed hydrophobic film to be formed, which pre-
vents corrosive materials from reaching the metal
surface.
Detergents and Dispersants
The terms "detergent" and "dispersant" are often
used interchangeably when discussing engine oils. If
[15]
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E-6
LUBRICATION
a distinction is made, detergents are normally con-
sidered for deposit control at high temperatures and
dispersants for controlling low-temperature sludge.
Detergents — When engines operate at high tem-
peratures, the engine oil is an important heat-
transfer fluid that prevents overheating of areas such
as piston rings, undercrowns, and skirts. Exposure to
these localized high temperatures and blowby gas
accelerates the rate of oil decomposition to produce
deposits19. These deposits can prevent free move-
ment of piston rings and keep them from forming
the desired seal between the piston and cylinder
wall. Varnish or lacquer deposits that can form on
the piston undercrown and skirts reduce the rate at
which the piston can transfer heat to the engine oil.
The products of high-temperature lubricant oxi-
dation are highly-acidic polar oxygenates which
have low solubility in mineral oil and a strong
affinity for other polar compounds and metal sur-
faces. They readily polymerize, and when trapped
in ring grooves they further decompose to hard
carbonaceous deposits19'24. Detergency as measured
in the ASTM Sequence VC Test is illustrated in
Figure 19-
Typical detergent additives are normal or basic
barium, calcium, or magnesium salts of substi-
tuted long-chain alkyl compounds. They react
with the highly-acidic deposit precursors to neutral-
ize them and keep them in suspension as very small
particles.
Dispersants — Engines operated under light-
duty, short-trip, stop-and-go conditions rarely reach
normal operating temperatures. This type of service
leads to formation of sludge which coats interior
engine parts and can block oil passages. Sludge is a
complex mixture of products from fuel combustion,
water, carbon, and oxidized oil that has agglomerated
and is no longer soluble in the engine oil. Typical
dispersants have a polar functional group appended
to a large hydrocarbon group. This enables them to
adsorb on contaminant particles such as soot or
lead halides and keep them in suspension so that
they cannot agglomerate to form sludge19-24.
Figure 20 illustrates dispersancy as measured in
taxi testing. In contrast to detergents, which are
often metal salts of organic acids, dispersants usually
do not contain metallic components and are there-
fore called "ashless". These additives are prepared
by incorporating polar functionality from amines,
amides, phosphorus esters or anhydrides with
methacrylate or olefin polymers. Substituted long-
chain r'-enyl succinimides are one of the many
classes of additives that have gained acceptance as
ashless dispersants.
Automatic transmission fluids are not required
to contend with the quantities of contamination
typical of engine oils, but they still must prevent
sludge formation. Wear debris from clutch plates
and oil decomposition products are kept from form-
ing sludge by the same types of ashless dispersants
used in engine oils25.
Friction Modifiers
Automatic transmissions, limited-slip differen-
tials, power take-off units and wet-brake systems
require lubricants with specific frictional properties
for proper clutch engagement. Some units require
a quick clutch lock-up, while others require a small
amount of slippage prior to lock-up for a smooth
engagement. A majority of the frictional require-
Before test. After test.
Dark areas are copper . . . light areas are lead.
Figure 18 — Scanning electron micrographs (870X magnification) showing lead corrosion of a copper-lead bearing in an L-38
engine test.
[16]
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LUBRICATION
E-7
Figure 19 — Detergency as measured in the ASTM Sequence VC Test.
Figure 20 — Dispersancy as measured in taxi testing.
[17]
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LUBRICATION
E-8
Additive Type
Pour Point
Depressant
Seal Swell
Agent
Viscosity Index
Improver
TABLE II
PERFORMANCE ADDITIVES
AUTOMOTIVE LUBRICANTS
Purpose
Enable lubricant to
flow at low temper-
atures
Swell elastomeric
seals
Reduce the rate of
viscosity change with
temperature
Typical Compounds
Alkylated naphthalene and
phenolic polymers, poly-
methacrylates
Organic phosphates,
aromatics, halogenated
hydrocarbons
Polymers and copolymers
of methacrylates, butadiene,
olefins and alkylated sty-
renes
Functions
Modify wax crystal formation to
reduce interlocking
Chemical reaction with elastomer
to cause slight swell
Polymers expand with increasing
temperature to counteract oil
thinning
mencs are determined by equipment design and the
materials used for clutch plates. The dynamic and
static coefficients of friction can also be modified
to provide the desired lock-up characteristics by
changing the viscosity of the lubricant and the
choice of the additives25'28.
Organic fatty acids have been used to provide a
smoother shift in automatic transmissions. Sulfur-
ized fatty acids and fatty amines have been used to
reduce the undesirable stick-slip conditions that
produce chatter and squawk sometimes associated
with clutch lock-up27. The additives used as
friction modifiers must not cause slippage once
lock-up has occurred, since excessive slippage would
produce high surface temperatures which could re-
sult in glazing of the clutch plates and ultimate fric-
tional failure of the transmission.
Performance Additives
Table II lists examples of these additives.
Pour Point Depressants
Mineral oils thin out at high temperatures and
thicken at low temperatures. These are natural prop-
erties of the oil that are determined by the crude
oil and the refinery processing which it receives.
Mineral oils selected for a particular lubricant
should allow that lubricant to remain fluid over the
entire temperature range it may encounter in serv-
ice. Paraffin wax present in most refined oils comes
out of solution at low temperatures in the form of
wax crystals. At these temperatures the oil itself is
still capable of flowing, but an interlocking network
of wax crystals will not permit flow.
Polymeric additives such as polymethacrylates,
or condensation products of chlorinated wax and
phenols can be used to interfere with wax crystal
growth and alter the formation of the interlocking
crystal network.
Seal-Swell Agents
Drive-train designs for transmitting power from
engines and gear cases involve the use of elastomeric
seals to prevent lubricant leakage and to exclude
dirt. Butadiene-acrylonitrile copolymers and silicone
elastomers are examples of two of the many com-
pounds commonly used for seals in drive-train com-
ponents25. The seals and the lubricants they come
in contact with mun be compatible. Significant
shrinkage or softening of the seals cannot be toler-
ated, but a slight swelling is often desirable to im-
prove contact with the moving shafts.
The chemical composition of the base oils them-
selves can affect seal swell, and this is usually taken
into consideration when formulating lubricants. If
the base oil does not provide sufficient swell, an
aromatic or organic phosphate additive is often used
to obtain the desired amount of swelling.
Viscosity Index (VI) Improvers
As mentioned in the section on pour depressants,
mineral oils become less viscous as their temperature
increases. The rate at which they thin out has been
described by a mathematical relationship between
their viscosities at 100°F (37.8°C) and 210°F
(98.9°C), which is referred to as viscosity index
(VI)28. Oils with a low VI exhibit a greater viscosi-
ty change with temperature than oils with a higher
VI. A lubricant that is expected to perform over
a wide temperature range must usually have a high
VI. The viscosity index of automotive engine oils
has received considerable attention because ease of
starting requires low viscosity at low temperatures,
but normal operation requires maintaining an ade-
quate fluid film near 300°F (149°C).
Mineral oils have been able to meet these wide-
temperature-range viscosity requirements through
use of high-molecular-weight polymeric additives
known as VI improvers. At low temperatures, these
polymers are barely soluble in the oil and exist as
closely coiled chains with little influence on vis-
cosity of the oil. As the temperature increases, the
polymer becomes more soluble and expands into
loose, random coils. These expanded polymers re-
strict movement of the oil molecules and serve to
reduce the rate at which oil thins out with increasing
temperature. Figure 21 illustrates the effect of a
VI improver on viscosity and viscosity index.
[18]
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LUBRICATION
E-9
Additive Type
Antifoamant
Antioxidant
Metal
Deactivator
TABLE III
LUBRICANT PROTECTIVE ADDITIVES
AUTOMOTIVE LUBRICANTS
Purpose
Prevent lubricant
from forming a
persistent foam
Retard oxidative
decomposition
Reduce catalytic
effect of metals
on oxidation rate
Typical Compounds
Silicone polymers, organic
copolymers
Zinc dithiophosphates, hindered
phenols, aromatic amines,
sulfurized phenols
Organic complexes containing
nitrogen or sulfur, amines,
sulfides and phosphites
Functions
Reduce surface tension to
speed collapse of foam
Decompose peroxides and
terminate free-radical reactions
Form inactive film on metal
surfaces by complexing with
metallic ions
Various methacrylates, olefin copolymers, and
copolymers of styrene have been used as VI im-
provers. The amount of thickening they provide de-
pends on the size of the polymer molecule. A larger
or higher-molecular-weight polymer of the same
Type will generally contribute more thickening.
Shear stability is another important property of VI
improvers. Larger long-chain polymers are more
likely to be broken apart by shear forces between
moving surfaces. Once this type of permanent
shearing takes place, the polymer contributes less
high-temperature thickening. Therefore, formula-
tion of high VI oils using polymeric VI improvers
requires selection of a polymer that will continue
to provide adequate high-temperature thickening
in service.
Lubricant Protective Additives
Examples of these additives are listed in Table III.
Antifoamants
All automotive lubricants which are subjected
to sufficient agitation will entrain air and produce
foam. This is undesirable because it increases ex-
posure of the lubricant to oxygen and thereby in-
creases the rate of oxidative decomposition. En-
trained air and foam also reduce lubricant efficiency
50 000
4.000
300
52
15
7
152 VI SAE 10W-40
95 VI SAE 40
95 VI SAE 10W
IOOT 210°F
TEMPERATURE
38't 99< ROOH (hydroperoxide) + R •
The process is further complicated by decomposi-
tion reactions:
ROOH -> RO • + OH •
which result in a variety of organic compounds such
as aldehydes, alcohols, ketones, and acids which may
further oxidize and react with each other to form
high-molecular-weight polymers. Some of these
polymers may be oil soluble, resulting in a viscosity
increase of the lubricant; others may be oil insoluble
and drop out as varnish or sludge.
Both the initiation and continuation of the oxi-
dation are materially affected by temperature fin
[19]
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LUBRICATION
TABLE IV
FUNCTIONS AND TYPES OF AUTOMOTIVE DRIVE-TRAIN LUBRICANT ADDITIVES
Performance Additives
Pour Point Depressants
Seal Swell Agents
Viscosity Index (VI) Improvers
Surface Protective Additives
Antiwear Agents
Corrosion Inhibitors
Detergents
Dispersants
Extreme Pressure (EP) Agents
Friction Modifiers
Rust Inhibitors
general, oxidation rates are roughly doubled for
each 10°C (18°F) rise in temperature], but may
also be catalyzed by light or by the presence of
various metals. Even minute amounts of some metals
may have a marked effect on oxidation.
The termination of the oxidation reaction may
result from the exhaustion of the oxygen supply—
which is not usual in lubrication systems where
there is normally at least some contact with the
atmosphere—or from the formation of end products
that are too stable to participate further in the oxi-
dation chain reaction:
2 R • -> RR
Oxidation inhibitors, or antioxidants, may func-
tion as chain-terminating agents by reacting with
free radicals to form stable products, by acting as
peroxide decomposers, or they may act as metal pas-
sivators to prevent catalytic effects. The chain ter-
minating additives are usually organic aromatic
amines, phenols, or sulfides. Those that inhibit the
catalytic effect of metallic ions are generally organic
sulfides, phosphites, or thiophosphates. Although
oxidation and corrosion inhibitors are frequently
referred to separately, many of the phosphorus- and
sulfur-containing compounds are effective in both
applications.
The entire matter of oxidation is affected by
many things, including the earlier-mentioned tem-
perature of the lubricant and by the materials of
construction of the equipment in which the lubri-
cant is used. It is also materially affected by the
inherent resistance of the lubricant itself to oxida-
tion. This resistance is affected by crude source and
refining process (which in turn affects the relative
amounts of paraffinic, aromatic and naphthenic
hydrocarbons). Because of these fundamental dif-
ferences, lubricant: respond differently to different
additives. The final choice of the additive must be
based, therefore, on actual tests in the lubricant to
be inhibited.
Metal Deactivators
In the discussion of oxidation inhibitors, metals
such as copper, iron, and lead were said to catalyze
oxidation. Additives that can form a coating on
metallic catalysts to prevent them from entering
Lubricant Protective Additives
Antifoamants
Antioxidants
Metal Deactivators
into reactions are variously referred to as metal de-
activators, metal passivators, or catalyst poisons. Ma-
terials previously covered as corrosion and rust in-
hibitors also function as metal deactivators, due to
their ability to form a coating on the metal surface.
Table IV summarizes and condenses the infor-
mation on the various groups and types of additives
used in automotive drive-train lubricants.
INDUSTRIAL LUBRICANT
ADDITIVES
This section examines some of the more common
additives used in industrial oils and greases. These
include oiliness, film strength, EP (extreme pres-
sure), and antiwear agents; corrosion inhibitors and
rust inhibitors; pour depressants and viscosity index
improvers; emulsifiers and demulsifiers; tackiness
agents; oxidation inhibitors; antifoamants; bacteri-
cides, bacteriostats, and fungicides; and miscella-
neous additives. These additives, either singly or
in various combinations, are used in a variety of
industrial lubricants. A few examples include metal
working lubricants, industrial greases, industrial
gear lubricants, transformer oils, hydraulic oils, re-
frigeration oils, turbine oils, compressor oils, rock
drill lubricants, paper machine oils, way lubricants,
and railway journal box oils.
Similar to automotive lubricant additives, indus-
trial lubricant additives can be classified into three
main functional types: those which (1) protect the
lubricated surface, (2) improve lubricant perform-
ance, and (3) protect the lubricant.
Surface Protective Additives
Examples of these additives are listed in Table V.
Oiliness, Film Strength, EP and Antiwear Agents
For many years, the film strength of straight min-
eral oils was adequate for many purposes. With
longer drain intervals and increased power output
and capacity for equipment of a given size, however,
the unit loading and resultant pressures on critical
parts increased. These higher loads led to the devel-
opment of so-called oiliness, film strength, extreme
pressure and antiwear agents. The basic purpose for
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LUBRICATION
E-ll
Additive Type
Oiliness Agent
Extreme Pres-
sure (EP) Agent
TABLE V
SURFACE PROTECTIVE ADDITIVES
INDUSTRIAL LUBRICANTS
Purpose
Reduce friction under
near-boundary con-
ditions
Prevent galling,
scoring and seizure
Antiwear Agent Reduce wear
Corrosion
Inhibitor
Rust Inhibitor
Prevent corrosive at-
tack on alloy bearings
or on other metallic
surfaces
Preventer reduce
rusting
Typical Compounds
High-molecular-weight compounds
such as fatty oils, oxidized waxes
or lead soaps
Sulfuri, chlorine-, and phosphorus-
containing materials, sometimes
with lead soaps
Organic phosphates and phos-
phites, zinc dithiophosphates
Organic compounds containing
active sulfur, phosphorus or nitro-
gen, such as phosphites, metal
salts of thiophosphoric acid, sul-
funzed waxes and terpenes
Sulfonates, amines, fatty oils,
oxidized wax, and halogenated
derivatives of some fatty acids
Functions
Adherence of polar mate-
rials to metal surfaces
Formation of low shear films
on metal surfaces at point
of contact
Exert a smoothing action to
form ultra-fine finishes
Inhibits formation of acidic
bodies or forms a protective
film over the metallic parts
Preferential adsorption of
polar, surface-active mate-
rials, neutralize corrosive
acids
the chemical compounds referred to by these gen-
eral classes is very similar. These materials are used
to (1) reduce friction, (2) prevent galling, scoring
and seizure, and ( 3) reduce or minimize wear31.
As long as the lubrication of a given piece of
equipment remains 'n the so-called hydrodynamic
region, the fluid film provided by oil alone is ade-
quate. Once boundary lubrication is reached, how-
ever,—that is, when the fluid film becomes very thin
—additives are required. Various terms such as oili-
ness agents, lubricity improvers, film strength en-
hancers, etc. have been used. The exact mechanism
of their functioning in each case is not fully under-
stood, due in part to difficulties of evaluation.
The term "oiliness" is used to indicate differences
in friction when different lubricants are used under
the same conditions. "Film strength" concerns the
loads that can be supported by a film. "EP" (extreme
pressure) agents are probably misnamed since the
formation of surface compounds of relatively low
shear strength is brought about by high tempera-
tures (which are experienced under extremely
high pressure conditions) rather than by hi^h
pressures as such. "Antiwear" agents apparently
function through a chemical polishing action on the
bearing surfaces.
Fatry acid esters and fatty alcohols are among the
commonly used oiliness agents. The EP agents are
generally compounds containing chlorine, sulfur,
and/or phosphorus. In the case of gear oils and
greases, the primary EP agents have been combina-
tions of sulfur-containing materials and lead soaps.
More recently, the heavy metals have become sus-
pect in many applications for toxicological reasons,
so the non-lead additives are now in wide use. Zinc,
phosphorus, and sulfur compounds such as tricresyl-
phosphate and zinc dithiophosphate have been
found to be effective as antiwear agents. Also, sulfur-
phosphorus systems containing no metals may be
effective.
The effectiveness of an additive depends on
the base fluid, other additives, and the operating
conditions. The best additive for one system may
not be effective in another. Also, multi-additive
packages must be balanced for a given product32.
Corrosion Inhibitors
These materials are added to lubricants to protect
against chemical attack of alloy bearings and metal
surfaces. As previously indicated, oxidation inhibi-
tors are also corrosion inhibitors to a degree since
they prevent—or at least delay—the formation of
oxidation products which may be chemically active
insofar as the metals present are concerned. Other
components, naturally present or added to various
lubricants, may also be chemically active. The use
of corrosion inhibitors is therefore common.
Corrosion inhibitors function by reacting chemi-
cally with the nonferrous metal components, e.g.
copper-lead or lead-bronze bearings, to form a cor-
rosion-resistant, protective film33.
The major classes of corrosion inhibitors in com-
mercial use at the present time include: (1) metal
diorganodithiophosphates, (2) metal diorganodi-
thiocarbamates, (3) sulfurized terpenes, (4) phos-
phosulfurized terpenes, and (5) heterocyclics such
as benzotriazole.
Rust Inhibitors
Although rusting is a form of oxidation, it is
being considered separately because rust inhibition
is concerned primarily with the protection of the
equipment itself rather than preventing oxidation
of the lubricant.
[21]
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LUBRICATION
E-12
TABLE VI
PERFORMANCE ADDITIVES
INDUSTRIAL LUBRICANTS
Additive Type
Pour Point
Depressant
Viscosity Index
(VI) Improver
Emulsifier
Demulsifier
Tackiness
Agent
Purpose
Lower the pour point
of lubricating oils
Lower the rate of
change of viscosity
with temperature
To give emulsions of
the water-in-oil or oil-
in-water type, depend-
ing on application
Loosen and break
stable emulsions
Increase adhesive-
ness of lubricant on
metal surfaces
Typical Compounds
Alkylated naphthylene or
phenols and their polymers,
methacrylate polymers
Polymerized olefins or iso-
olefins, butylene polymers,
alkylated styrene polymers,
polymethacrylate
Soaps of fatty acids, sul-
fonic acids or naphthenic
acids
Heavy metal soaps, alkaline
earth sulfonates
High molecular weight
polymers, aluminum soaps
of unsatu rated fatty acids
Functions
Modification of wax crystals to
prevent growth with accompany-
ing solidification at low tempera-
tures
Because of differences in solu-
bility, viscosity at high tempera-
ture is raised more than viscosity
at low temperature
Surface-active agents change
interfacial tension
Lower emulsion stability
Increases viscosity of lubricant
and imparts adhesive character-
istics
Moisture due to machine operating conditions,
for example in circulating systems of steam
turbines, steel mills, paper machines, etc., may
be present either as free water or as entrain-
ment in the lubricant. Rust inhibitors prevent water
from penetrating the protective oil film. This is
accomplished by improving the ability of the oil
to adhere tenaciously to the metallic machine sur-
faces (ball and roller bearings, steel shafting, gear
teeth, etc.) or, if the amount of moisture is small
and operations permit, by emulsifying the moisture
so that it does not contact the metal surfaces.
Typical of the materials used for rust inhibition
are alkenylsuccinic acids and their derivatives, alkyl-
thioacetic acid derivatives, substituted imidazolines,
amine phosphates, and metal and amine sulfonates.
In the case of lubricating greases, if only small
amounts of water are present, sodium soap greases
have generally very good rust inhibition because
of their ability to absorb and emulsify the
water. If large quantities of water are involved, as
for example in steel mill operations, sodium soap
greases are not satisfactory because of high water
washout losses. In these cases, water-repellent greases
are used, sometimes with additives to improve water
repellency. Certain organic silicone polymers and
some aliphatic amines are useful in this type of
application.
Performance Additives
Examples of these additives are listed in Table
VI.
Pour Depressants and Viscosity
Index (VI) Improvers
Industrial lubricants are at times used under low
temperature conditions. The same general types of
additives are used as for automotive oils, i.e., various
polymers to modify wax crystal growth or to change
the viscosity-temperature profile of the lubricant.
Emulsifiers
In most lubrication applications, emulsification
is an undesirable characteristic. In some specific
types of usage, however, lubricants are purposely
compounded with emulsifying agents. In the case
of the fire-resistant hydraulic fluids, water-in-oil
emulsions are desired. In this case the primary
function of the fluid is still lubrication—the water
incorporated in the fluid serves primarily to de-
crease the flammability of the oil. These products
are, therefore, safer for use in mines and other loca-
tions where low flammability is needed for safety
reasons.
In the metal working area—cutting and grinding
of metals—the primary need is for cooling. In this
case, oil-in-water emulsions are desired. The oil,
with added emulsifiers, is normally sold as such and
the product is emulsified with water at the point
of use.
A wide variety of emulsifiers have been used. For
water-in-oil emulsions, typical emulsifiers include
ethylene oxide condensation products, some metal
sulfonates, derivatives of polyhydroxy alcohols such
as sorbitol, and sulfosuccinates. For oil-in-water
emulsions, i.e., "soluble oils," surface-active agents
which reduce the interfacial tension sufficiently so
that the oil can be finely dispersed in water are used.
Soaps of fatty acids, sulfonic acids, rosins, or naph-
thenic acids have been used for this purpose. In
any case, a delicate balance between emulsifier ratios
and alkalinity must be achieved; this must be
established for each system and cannot be broadly
predicted.
[22]
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LUBRICATION
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TABLE VII
LUBRICANT PROTECTIVE ADDITIVES
INDUSTRIAL LUBRICANTS
Additive Type
Antioxidant
Antifoamant
Bactericide,
Bactenostat
and Fungicide
Purpose
Prevent varnish and
sludge, prevent cor-
rosion of alloy bear-
ings
Prevent formation of
stable foam
Control of bacteria
and fungi to control
odor, emulsion break-
ing and metal staining
Typical Compounds
Organic compounds containing
sulfur, phosphorus or nitrogen,
i.e., organic sulfides, amines or
hydroxy sulfides
Silicone polymers, organic poly-
mers
Certain alcohols, aldehydes,
phenols and chlorine-containing
compounds
Functions
Terminates oil oxidation
reactions by the formation
of inactive compounds or by
taking up oxygen
Change interfacial tension
to permit coalescence of
small bubbles; large bub-
bles separate faster
Prevention of growth of
bacteria and fungi
Demulsifiers
In those cases where emulsification with water is
undesirable, demulsiners may be used. Frequently,
these are heavy metal soaps or alkaline earth sulfo-
nates which are antagonistic to emulsion formation
in the system involved.
Tackiness Agents
In some cases it is highly desirable that lubricants
cling very closely to the lubricated parts and not run
off. Good examples would be in the lubrication of
textile machinery where runoff would be deleterious
to the product, or in the case of track roll lubrica-
tion where bearings tend to be loose fitting. High-
molecular-weight polymers and some aluminum
soaps of high-molecular-weight fatty acids have
been used successfully as additives in such appli-
cations.
Lubricant Protective Additives
Table VII lists a number of these addi-
tives.
Oxidation Inhibitors (Greases)
The oxidation inhibition of greases presents sev-
eral problems not normally found with industrial
lubricating oils. Greases are thickened oils; the
thickeners most commonly used are metallic soaps
of fatty materials. The presence of the fatty mate-
rial, particularly where there is some degree of un-
saturation (i.e., where double bonds are present
in the molecule), makes highly vulnerable sites
available for the initiation of the oxidation reaction.
Aromatic amines serve well as oxidation inhibitors
for greases.
Antifoamants
One of the problems that has been experienced
for many years with lubricating oils is excessive
foam. There are many situations where petroleum
lubricants are used in which entrainment of air or
other gases is inevitable. Unless these gases can be
released, a foam results. Foams may displace oil
from the system, causing improper functioning of
pumps, reduced oil flow, enhanced oxidation of the
lubricant, and other difficulties.
Silicone polymers have been used very success-
fully for the release of foam in many situations. In
some cases, however, these materials may result in
higher air entrainment in the liquid. In these cases,
other antifoamants, such as some of the polyacrylates
and other organic polymers may be more effective.
Bactericides, Bacteriostats and Fungicides
The problem of bacterial control is closely allied
to the problem of emulsion stability. Bacteria in
large systems containing soluble oil type oil-in-
water emulsions are at times a problem. This is
particularly true in cases where weekend shut-
downs are involved. Bacterial growth results in
bad odors and emulsion degradation. The com-
mon bacteria are pseudomonas oleovorans and
similar types; the emulsions are normally not af-
Additive Type
Dye
Odorant
TABLE VIM
MISCELLANEOUS ADDITIVES
INDUSTRIAL LUBRICANTS
Purpose
Provide distinctive or
attractive color
Provide distinctive or
pleasant odors or mask
undesirable odors
Typical Compounds
Oil-soluble compounds
with high coloring power
Oil-soluble synthetic
perfumes
Functions
Highly colored materials dis-
solve to impart color
Small amounts of highly fra-
grant substances impart odor
to lubricants
[23]
-------
E-14
LUBRICATION
TABLE IX
FUNCTION AND TYPES OF INDUSTRIAL LUBRICANT ADDITIVES
Surface Protective
Additives
Oiliness Agents
Extreme Pressure
(EP) Agents
Antiwear Agents
Corrosion Inhibitors
Rust Inhibitors
Performance
Additives
Pour Point Depressants
Viscosity Index (VI)
Improvers
Emulsifiers
Demulsifiers
Tackiness Agents
Lubricant Protective
Additives
Antioxidants
Antifoamants
Bactericides, Bacteriostats
and Fungicides
Miscellaneous
Additives
Dyes
Odorants
fected by pathogenic varieties. To control bacteria
and fungi, antiseptics and bactericides containing
certain alcohols, phenols, and chlorine-containing
materials have been used.
Miscellaneous Additives
A complete discussion of all the areas where en-
hancement of lubricant properties or the achieve-
ment of desired qualities have been brought about
by the use of additive materials is beyond the scope
of this article. A few of the other areas include the
use of dyes to obtain a desired or distinctive color
or a uniformity of color, and odorants to provide a
distinctive odor or to mask undesirable odors. Ex-
amples of these are listed in Table VIII.
Table IX summarizes and condenses the informa-
tion on the various groups and types of additives
used in industrial lubricants.
One additional item should at least be given men-
tion. It should be evident from the foregoing that
choosing addifves for a lubricant to accomplish a
specific purpose is not something that can be done
in a haphazard way. Many times additives may have
interacting effects so that undesirable side reactions
may be experienced if additives are mixed without
full consideration of these reactions. Since it is fre-
quently necessary to use a number of different addi-
tives, the total additive "package" must be carefully
balanced. The user of quality lubricants can rest
assured that much care and testing has gone into
the correct balancing of the total package.
SUMMARY
The petroleum industry makes extensive use of
additives throughout its operation. This article has
presented in condensed form, the rationale for using
additives in fuels, automotive drive-train lubricants,
and industrial lubricants. Enormous amounts of
time, scientific talent and money are spent formulat-
ing and evaluating additives for use in these prod-
ucts. All this is done to insure that a customer will
be able to obtain a petroleum product that satisfies
his performance requirements.
REFERENCES
16. W. M. Cummings, "Fuel and Lubricant Additives—I,"
LUBRICATION, Vol. 63, No. 1,1977.
17. Chemical Economics Handbook, Stanford Research
Institute, 1973.
18. "What You Should Know About Lubricant Addi-
tives," Power, Sept. 1969.
19. K. L Kreuz, "Gasoline Engine Chemistry," LUBRI-
CATION, Vol. 55, No. 6, 1969.
20. R. S. Fein and K. L. Kreuz, "Lubrication and Wear,"
LUBRICATION, Vol. 51, No. 6,1965.
21. R. S. Fein and F. J. Villforth, Jr., "Lubrication Funda-
mentals," LUBRICATION, Vol. 59, Oct.-Dec. 1973.
22. A Schilling, Automotive Engine Lubrication, England,
Scientific Publications (G.B.) Ltd., 1972.
23. C. V. Smalheet and R. K. Smith, Lubricant Additives,
Cleveland, Lezins-Hiles Co., 1967.
24. K. L. Kreuz, "Diesel Engine Chemistry," LUBRICA-
TION, Vol. 56, No. 6, 1970.
25. R. G. Lacoste, "Automatic Transmission Fluids," LUB-
RICATION, Vol. 54, No. 1, 1968.
26. N. A. Nann and F. H. Pinchbeck, "Automatic Trans-
mission Shift Quality," LUBRICATION, Vol. 52,
No. 7, 1966.
27. R. L. Kostelak, "Limited Slip Differentials," LUBRI-
CATION, Vol. 56, No. 4, 1970.
28. R. Pomatti, "Viscosity," LUBRICATION, Vol. 52,
No. 3, 1966.
29. S. Ross, "Mechanism of Foam Stabilization and Anti-
foam Action," Chemical Engineering Progress, Vol.
63, No. 9,1967.
30. C. Walling, tree Radicals in Solution, New York,
John Wiley & Sons, Inc., 1957.
3I.E. F. Koenig, "Additives with a Purpose," WBRICA-
T/ON, Vol. 43, No. 3, 1957.
32. E. C. Fitch, "The Evaluation of Anti-Wear Additives
in Hydraulic Fluids," Wear, Vol. 36, p. 255, 1976.
33. C. V. Smalheer, "Interdisciplinary Approach to Liquid
Lubricant Technology," NASA SP-318, p. 445, 1973.
[24]
-------
FUEL AND LUBRICATING OILS FOR DETROIT DIESEL ENGINES
This bulletin presents guidelines for the fuels ond lubricants best suited for good performonce
and long life in Detroit Diesel engines.
DIESEL FUEL OILS
GENERAL CONSIDERATIONS
The quality of fuel oil used for high-speed diesel engine
operation is a very important factor in obtaining
satisfactory engine performance, long engine life, and
acceptable exhaust.
Fuel selected should be completely distilled material.
That is, the fuel should show at least 98% by volume
recovery when subjected to ASTM D-86 distillation.
Fuels marketed to meet Federal Specification VV-F-
800 (grades DF-1 and DF-2) and ASTM Designation
D-975 (grades 1-D and 2-D) meet the completely dis-
tilled criteria. Some of the general properties of VV-
F-800 and ASTM D-975 fuels are shown below.
FEDERAL SPECIFICATION & ASTM
DIESEL FUEL PROPERTIES
Specification or
Classification Grade
Flash Point, mm.
Carbon Residue (10%
residuum 1. % max
V»'ater & Sediment. % by
vol . max.
Ash. /» by wt.. max.
Distillation Temperature.
90% by vol. recov cry, mm.
max.
End Point, max.
Viscosity 100°F(38°C)
Kinematic, cs, mm.
Sa\ bolt, SUS, mm.
Kinematic, cs, max
Saybolt. SUS. max.
Sulfur. % by wt , max
Ceiane No.
VV-F-
800
1)F-1
104° F
40° C
0.15
001
0005
572°F
(300°C)
626°F
(330°C)
1.4
3.0
050
45
ASTM
D-975
I-D
100° F
38° C
0.15
trace
0.01
550°F
(28S°C)
1.4
25
344
0.50
40
VV-F.
800
DF-2
122° F
50° C
0.20
0.01
0.005
626°r
(330°C)
671°F
(355°C)
2.0
4.3
0.50
45
ASTM
D-975
2-D
125° F
52°C
0.35
0.05
0.01
540°F
(282°C)
640°F
(338°C)
2.0
32.6
43
40.1
0.50
40
jipjrne.su
__
sidered satisfactory for_Dc.trou__Diesel engines, how-
e\~crr~"soTne may ~T>e acceptable. (See "DETROIT
NOTE: DetroiTTJiesfl AlTisonlloe^CTTorTCcomnicnd
Ihe use of drained lul>ricnlin<; oil as a diesel fuel oilL
Furthcrniore^~TJcTroTl TJTesol Allison «ill not be re-
sponsible for any engine detrimental effects which it
determines resulted from (his practice,
All diesel fuel oil contains a certain amount of sulfur.
Too high a sulfur content results In
wear clue to acicTTniTtTf-up in the rubricating oil. 1-or
nost satisfactory eng7nc[iT£TiTeTs^containTiTg less
.nan 0.5% sulfur should be used.
Fuel oil should be clean and Iree of contamination.
"Mmaye tanks should be inspected regularly for dirt.
waier or water-emulsion sludge, and cleaned if con-
taminated. Storage instability of the fuel can lead to
the formation of varnish or sludge in the tank. The
presence of these contaminants from storage instability
must he icsolied with the fuel supplier.
t IQ^ft r,.">->rnl Mrtnrs (1nrnnr,?finn
DETROIT DIESEL FUEL OIL SPECIFICATIONS
Detroit Diesel Allison designs, develops, and manu-
factures commercial diesel engines to operate on die-
sel fuels cla-ssified by the ASTM as Designation D-975
(grades 1-D and 2-D). These grades are very similar
to grades DF-1 and DF-2 of Federal Specification
VV-F-800. Residual fuels and furnace oils, generally.
are not considered satisfactory for Detroit Diesel
engines. In some regions, however, fuel suppliers may
distribute one fuel that is marketed as eithei diesel fuel
(ASTM D-975) or domestic heating fuel (ASTM D-396)
sometimes identified as furnace oil. In this case, the
fuel should be investigated to determine whether the
properties conform with those shown in the "FUEL OIL
SELECTION CHART" presented in this specification.
The "FUEL OIL SELECTION CHART" also will serve
as a guide in the selection of the proper fuel for various
applications. The fuels used must be clean, completely
distilled, stable, and non-corrosive. DISTILLATION
RANGE. CETAN'E NUMBER, and "sTJOTiR COiv
TENT'are~three ot the mosrimportant nt^perties of
diesel fuels that must be controlled to injure optimum
combustion and minimum wear, hngine spTeu, io"3,
"and ambieri Temperature mtluence the selection of
fuels with respect to distillation range and cetane
number. The sulfur content of the fuel must be as low
as possible to avoid excessive deposi; fnrmntinn pv^.
mature wear, and to minimi^ the sulfur dioxide f»-
r">ustert into the afmosnhe.re.
To assure that the fuel you use meets the required
properties, enlist the aid of a reputable fuel oil supplier.
The responsibility for clean fuel lies with the fuel
supplier as well as the operator.
During cold weather engine operation, the cloud point
(the temperature at which wax crystals benin to form
in diesel fuel) should be 10°F (6°C) below" the lowest
expected fuel temperature to prevent clogcing of the
fuel filters by wax crystals.
At temperatures below —20°F ( —29°C). consult an
authorized Detroit Diesel Allison service outlet, since
particular attention must be given to the cooling sys-
tem, lubricating system, fuel system, electrical system,
and cold weather starting aids for efficient encme
starting and operation.
FUEL OIL SELECTION CHART
Typical
Application
City Buses
All Other
Applications
General Fuel
Classification
No. 1-D
Winter No. 2-D
Summer No. 2-D
Flnnl
Boilinq
Point
(Max.)
550°F
(2«8°C)
675 °F
675°F
(3,r)7°C)
Cetane
No.
(Mm.)
45
45
40
Snlfur
Conttnt
(Max.)
0.30%
050%
0 50%
NOTE: When prolonpi-rf iillinp^^jj-iiwk or rold
Heather conditions below 32°F (U°C) arc encoun-
tered, the use of lighter dUfillnte fuels may be more
practical. The same consideration must he made
when operating at altitudes above 5,(KK> ft.
-------
E-16
DIESEL LUBRICATING OILS
GENERAL CONSIDERATIONS
All diesel engines require heavy-duty lubricating oils.
Basic requirements of such oils are lubricating quality,
high heat resistance, and control of contaminants.
LUBRICATING QUALITY. The reduction of friction
and wear by maintaining an oil film between moving
parts is the primary requisite of a lubricant. Film
thickness and its ability to prevent metal-to-metal
contact of moving parts is related to oil viscosity. The
optimums for Detroit Diesel en£ings_arp i.sw^j™^
SAE 40 or 30 weight.
HIGH HEAT RESISTANCE. Temperature is the most
important factor in determining the rate at which
deterioration or oxidation of the lubricating oil will
occur. The oil should have adequate thermal stability
at elevated temperatures, thereby precluding forma-
tion of harmful carbonaceous and/or ash deposits.
CONTROL OF CONTAMINANTS. Ihe_pjston and
compressjonjjngs must ride on a film of oil to minimize
wear and prevent cylinder seizure. At normal rates olf
consumption, oil reaches a temperature zone at the"
"Gpperpart of the piston where rapid oxidation and
"Carbonization can occur. In addition, as oil circulates
Through the engine, it is continuously contaminated by
soot, acids, and water originating from combustion.
Until they are exhausted, detergent and dispersant addi^
lives aid in keeping sludge and varnish from depositing
on engine parts. But such additives in excessive quan-
tities canjresult in detnmenial ash deposits. If abnormal
amounts of insoluble deposits torm, particularly on the
piston in the compression ring area, early engine failure
may result.
Oil that is carried up the cylinder liner wall is normally
consumed during engine operation. The oil and addi-
tives leave carbonaceous and/or ash deposits when sub-
jected to the elevated temperatures of the combustion
chamber. The amount of deposits is influenced by the
oil composition, additive content, engine temperature,
and oil consumption rate.
DETROIT DIESEL LUBRICATING
OIL SPECIFICATIONS
OIL QUALITY
OIL QUALITY is the responsibility of the oil supplier.
(The term oil supplier is applicable to refiners, blend-
ers, and rebranders of petroleum products, and does
not include distributors of such products.)
There are hundreds of commercial crankcase oils mar-
keted today. Obviously, engine manufacturers or users
cannot completely evaluate the numerous commercial
oils. The selection of a suitable lubricant in consulta-
tion with a reliable oil supplier, observance of his oil
drain recommendations (based on used oil sample
analysis and experience) and proper filter maintenance.
will provide the best assurance of satisfactory oil
performance.
Detroit Diesel Allison lubricant recommendations are
based on general experience with current lubricants of
various types and give consideration to the commer-
cial lubricants presently available.
RECOMMENDATION
Detroit Diesel engines have given optimum perform-
ance and experienced the longest service life with the
following oil performance levels having the ash limits
and zinc requirements shown.
15W-40 MULTIGRADE LUBE OIL
Detroit Diesel Allison now approves and recommends
the use of the new generation 15W-40 lubricating oils,
providing the following ash limits, zinc requirements,
oil performance levels, and conditions are met:
1. The sulfated ash (ASTM D-874) content of the lubri-
cant shall not exceed 1.000% by weight, except
lubricants that contain only barium detergent-
dispersant salts where 1.5% by weight is allowed".
2. The lubricant shall meet the performance require-
ments shown in API Service Classifications CD/SE.
3. The zinc content (zinc diorganodithiophosphate) of
all the lubricants recommended for use in Detroit
Diesel engines shall be a minimum of 0.07% by
weight. However, the zinc requirement is waived
where EMD lubricants are used.
4. Evidence of satisfactory performance in Detroit
Diesel engines has been shown to the customer and
to Detroit Diesel Allison by the oil supplier.
10W-30, 20W-40 & OTHER MULTIGRADE OILS
Detroit Diesel Allison does NOT approve any multi-
grade oils, except the new generation 15W-40 lubricants
previously described. Although lubricants such as
10W-30 and 20W-40 are commercially available, the
performance of their additive systems has not been
demonstrated in Detroit Diesel engines. Since prop-
enies_such_as sulfated ash are_affectedI injormulating
these multigrade compounds, their use canrToT^bfr-X.
approved.
SAE-40 & SAE-30 SINGLE GRADE LUBRICANTS
Detroit Diesel Allison continues to approve SAE-40
and SAE-30 lube oils, providingjhey meet the 1.000%
maximum "suTfated"ash limit, the 0.07% by weight mini-
murn__zinc content, and the following API Service
Classifications: ' — • •—
i
API Letter Code
Service
Classification
CB
CC
CD/SC
CD
CC/SE
Numerous
MUit.ry
Specification
MIL-L-2104A (Supplement 1)
M1L-L-21WB
MIL-L-2104C
MIL-l^t5199B (Series 3)
MIL-1^46152
Universal
SAE
Grade
40 or 30
40 or 30
40 or 30
40 or 30
40 or 30
40 or 30
MIL-L-46167 ARCTIC LUBE OILS
FOR NORTH SLOPE & OTHER
EXTREME SUB-ZERO OPERATIONS
Lubricants meeting this specification are used in
Alaska and other extreme sub-zero locations. Generally.
they may be described as 5W-20 multigrade lubricants
made up of synthetic base stock and manifesting low
volatility characteristics. Although they have been used
-------
' successfully in some severe cold regions. Detroit
Diesel Allison does not consider their use as desirable
as the use of 15W-40 (new generation), SAE-40, or
SAE-30 oils with auxiliary heating aids. For this reason,
they should be considered only where engine cranking is
a severe problem and auxiliary heating aids are not avail-
able on the engine.
EMD(RR)OILS
Lubricants qualified for use in Electro-Motive Division
(EMD) diesel engines may be used in Detroit Diesel
engines provided the sulfated ash (ASTM D-874) con-
tent does not exceed 1.000% by weight. These lubricants
are frequently desired for use in applications where
both Detroit Diesel and Electro-Motive powered units
are operated. These fluids may be described as SAE-40
lubricants that possess medium Viscosity Index prop-
erties and do not contain any zinc additives.
SYNTHETIC OILS
Synthetic lubricants may be used in Detroit Diesel en-
gines provided the ash limit, ^i^c_jr^uirernents1 and
specified oil perlormance levels (for example. CD/SE
or MlE-DrZT04B~reCc.) shown" elsewhere in this specifi-
cation are met. Viscosity grades 15W-40 or SAE-40 or
SAE-30 are recommended.
EVIDENCE OF SATISFACTORY PERFORMANCE
Detroit Diesel Allison has referred to evidence of satis-
factory performance in its lubricant specifications.
Detroit Diesel Allison uses controlled field test oil evalu-
ation programs to determine the performance of lubri-
cants. The following briefly describes one method
Detroit Diesel Allison uses to evaluate lubricating oil
performance. This method may be used as a guideline
for oil suppliers with candidate lubricants for Detroit
Diesel engines.
I. Select five (5) highway truck (72.000 Ibs. GCW) units
in the same fleet powered by Detroit Diesel engines.
Operate these on the candidate 15VV-40 motor oil for
200,000 miles.
2. Select five (5) "sister" highway trucks in the same
fleet to operate on a reference SAE-30 or SAE-40
grade lubricant having a history'of good performance
in Detroit Diesel engines.
3. Operate the ten (10) oil test engines for 200.000 miles
each. Monitor the oil and fuel consumption during
the test period. Record any serious mechanical prob-
lems experienced. Disassemble all ten (10) engines at
the conclusion of the 200.000 mile period and com-
pare the following:
• Ring sticking tendencies and/or ring conditions.
• Piston skirt and cylinder liner scuffing.
• Exhaust valve face and stem deposits.
• Overall wear levels.
4. The results obtained from a new candidate 15W-40
lubricant should be comparable to or better than
those obtained from SAE 30 or 40 oils.
ENGINE OIL CLASSIFICATION SYSTEM
The American Pelioleum Institute (API), the Society of
Automotive Engineers (SAE), and the American Socieiy
for Testing and Materials (ASTM) jointly have devel-
oped the present commercial system for designating and
E-17
identifying motor oil classifications. The table below
shows a cross-reference of current commercial and
military lube oil identification and specification systems.
CROSS REFERENCE OF LUBE OIL
CLASSIFICATION SYSTEM
AHC
Code
loiters
CA
CB
CC
CD
SA
SB
SC
SD
SE
Comparable Military or Commercial Industry Specification
MIL-L-2104A
Supplement 1
MII.-L-2104B (see note below)
M1L-L-45199B (Series B)
M1L-L-46152 (supersedes MIL-L-2104B for Military only.)
MIL-L-2I04C (supersedes MIL-L^(5199B (or Military only.)
none
none
Auto passenger car 1964 MS oils — obsolete system
Auto passenger car 196S MS oils — obsolete system
Auto passenger car 1972 MS oils — obsolete system
t Oil performance meets or exceeds that of CC and SE oils.
• Oil performance meets or exceeds that of CD and SC oils.
NOTE: MIL-L-2104B lubricants are obsolete for Mili-
tary service applications only.
MIL-L-2104B lubricants are currently marketed and
readily available for commercial use.
Consult the following publications for complete
descriptions:
1. Society of Automotive Engineers (SAE) Technical
Report J-;33a.
2. Federal Test Method Standard 791a.
OIL CHANGES
Oil change intervals are dependent upon the various
operating conditions of the engines and the sulfur
content of the diesel fuel used. Oil drain intervals in
all service applications may be increased or decreased
with experience using a specific lubricant, while also
considering the recommendations of the oil supplier.
Generally, the sulfur content of diesel fuels supplied
throughout the U.S.A. and Canada are low (i.e.. less
than 0.5% by weight - ASTM D-129 or D-1552 or
D-2622). Fuels distributed in some overseas locations
may contain higher concentrations of sulfur, the use of
which will require reduced lube oil drain intervals.
Highway Trucks & Inter-City Buses
(Series 71 and 92 Naturally Aspirated and Turbocharged
Engines)
For highway trucks and buses used for inter-city
operation, the oil change interval is 100,000 miles. The
drain interval may be extended beyond this point if
supported by the results obtained from used lube oil
analysis; it is recommended that you consult with your
lube oil supplier in establishing any drain interval ex-
ceeding 100,000 miles.
City Transit Conches and Pick-Up and Delivery Truck
Service (Scries 53, 71 and 92 Naturally Aspirated and
Turbocharged Engines)
For city transit coaches and pick-up and delivery truck
service, the oil change interval is 12.500 miles. The oil
drain interval may be extended beyond 12.500 miles
if supported by used oil analyses.
-------
Industrial and Marine
(Scries 53, 71, and 92 Naturally Aspirated and Turbo-
charged Engines)
Series 53, 71, and 92 engines, in industrial and marine
service, should be started with 150-hour oil change
periods. The oil drain intervals may be extended if
supported by used oil analyses.
Large Industrial and Marine
(Scries 149 Naturally Aspirated and Turbocharged
Engines)
The recommended oil change period for naturally
aspirated Series 149 engines is 500 hours, while the
change period for turbocharged Series 149 engines is
300 hours. These drain intervals may be extended i!
supported by used oil analyses.
Used Lube Oil Analysis Warning Values
The presence of ethylene giycol in the oil is damaging to
the engine. Its presence and need for an oil change and
for corrective maintenance action may be confirmed by
giycol detector kits which are commercially available.
Fuel dilution of the oil may result from loose fuel con-
nections or from prolonged engine idlmg^A_fue^dilution
exceeding 2.5% of volume jndjcates an irnmed|ate_neecT
for an_jn_cJiajT^e_aiidlcorTective maintenance action .
Fuel dilution may be confirrjTed^by_ASTM D-322 test
by oil suppliers or independent
' " "
In addition to the above considerations, if any of the
following occur, the oil should be changed:
1. The viscosity at 100° F. of a used oil sample is 40%
greater than the viscosity of the unused oil measured
at the same temperature (ASTM D-445 and D-2161).
2. The iron content is greater than 150 parts per million.
3. The coagulated pentane insolubles (total contamina-
tion) exceed 1.00% by weight (ASTM D-893).
4. The total base number (TBNi is less than 1 .0 (ASTM
D-664). Note: The sulfur content of the diesel fuel
used will influence the alkalinity of the lube oil. With
high sulfur fuels, the oil drain interval will have to be
shortened to avoid excessive acidity in the lube oil.
LUBE OIL FILTER ELEMENT CHANGES
Full-Flow Filters
A full-flow oil filtration system is used in all Detroit
Diesel engines. To ensure against physical deterioration
of the filter element, it should be replaced at a maximum
of 25.000 miles for on-highway vehicles or at each oil
change period, whichever occurs first. For all other
applications, the filter should be replaced at a maximum
of 500 hours or at each oil change period, whichever
occurs first.
By-Pass Filters E~18
Auxiliary by-pass lube oil filters are not required on
Detroit Diesel engines
PUBLICATION AVAILABLE SHOWING
COMMERCIAL "BRAND" NAME LUBRICANTS
A list of "brand" name lubricants distributed by the
majority of worldwide oil suppliers can be purchased
from the Engine Manufacturers Association (EMA).
The publication is titled. EMA Lubricating Oils Data
Book for Heavy-Duty Automotive and Industrial En-
gines. The publication shows the brand names, oil
performance levels, viscosity grades, and sulfated ash
contents of most "brands" marketed.
ENGINE MANUFACTURERS ASSOCIATION
111 EAST WACKER DRIVE
CHICAGO, ILLINOIS 60601
STATEMENT OF POLICY ON FUEL AND
LUBRICANT ADDITIVES
In answer to requests concerning the use of fuel and
lubricating oil additives, the following excerpt has been
taken from a policy statement of General Motors
Corporation:
"It has been and continues to be General Motors
policy to build motor vehicles that will operate satis-
factorily on the commercial fuels and lubricants of
good quality regularly provided by the petroleum
industry through retaiToutlets. "
Therefore, Detroit Diesel Allison does not recommend
the use of any supplementary fuel or lubricant additives.
These include all products marketed as fuel condi-
tioners, smoke suppressants, masking agents, reodo-
rants, tune-up compounds, top oils, break-in oils,
graphitizers. and friction-reducing compounds.
NOTE: The manufacturer's warranty applicable to
Detroit Diesel engines provides in part that the pro-
visions of such warranty shall not apply to any engine
unit which has been subject to misuse, negligence or
accident. Accordingly, malfunctions attributable to
neglect or failure to follow the manufacturer's fuel
or lubricating recommendations may not be within
the coverage of the warranty.
SERVICE AND INSPECTION INTERVALS
Generally, operating conditions will vary for each
engine application, even with comparable mileage or
hours and therefore, maintenance schedules can vary.
A good rule of thumb for piston ring, and liner inspec-
tions, however, would be at 45,000 miles or 1500 hours
for the first such inspection and at 30.000 miles or 1000
hour intervals thereafter.
Detroit Oiesei Allison
Division of General Motors Corporation
13400 West Outer Drive Detroit, Michigan 48228
In C»ni4» DtMtl 0-vition. Cineul Mow) of Cintdl, Limtltd. London. Onll'to
-------
E-19
CATERPILLAR TRACTOR CO.
Pcoria. Illinois 61629
June 19, 1979
Mr. Thomas M. Baines
Characterizatioh & Applications Branch
U.S. Environmental Protection Agency
Ann Arbor, MI 48105
Dear Tom:
Oil Samples for Nitrosamines Evaluation
This letter is to confirm that we are interested in participating in the EPA
diesel crankcase emission characterization program. We look forward to coop-
erating with EPA in this matter but first we would like* to see the results of
the MIT evaluation of Dr. Fine's nitrosamine measuring technique.
As you have discussed with R. D. McDowell, the oil samples we will provide are
as indicated by the following table:
Engine
3208 NA
3406 BIT
3406 DITA
Oil Type
AMOCO 300
(15W40)
Chevron RPM
DELO 400
(30W)
Chevron RPM
DELO 300
(30W)
Approximate Sampling Schedule
As a Fraction of Change Period
New 1/3 2/3 Drain
New- 1/3- 2/3 Drain
New 1/3 2/3 Drain
As shown by the chart, you will be receiving four samples from each engine for
a total of 12 samples. The first two engines are operating in trucks owned by
a locally based trucking company. The third engine (3406 DITA) will be operat-
ing in the lab on an on-highway truck cycle dynamometer test. Along with the
oil samples we will supply as much of the requested information as possible. We
shall initiate supplying the oil samples whenever you indicate your contractor
can accept the samples.
If you have any questions or comments, please contact R. D. McDowell or me.'
Verw truly yours,
JCHafele
Ph: (309) 675-5362
sdc
dssions Control Manager
G.O.
-------
TEXACO ,NC.
135 EAST 42NO STREET. NEW YORK, NEW YORK 10017
RETURN REQUESTED
BULK RATE
U. S. POSTAGE
PAID
Fairview, N. J.
Permit No. 217
• fi-
ll, ij. Qirrr.i.i/ui .nt.
JJOUTIIWIiK'L1 HKMKAIUIII
i'. 0. UimVJKH :!ll^in
BAH AIITOUK), TX Y
.-i
TEXACO INC. REGIONAL OFFICES
ATLANTA HOUSTON
59 Executive Park South N.E. 4800 Fournace Place
Atlanta, Ga. 30329 404321-4411 Bellaire, Texas 77401
713666-8000
CHICAGO LOS ANGELES
332 So. Michigan Avenue 3350 Wilshire Blvd.
Chicago, 111.60604 312427-1920 Los Angeles, Ca. 90010 213385-0515
PHILADELPHIA
1040 Kings Highway N.
Cherry Hill, NJ. 08034 609 667-3800
Texaco Petroleum Products are distributed throughout the United States, Latin
America, United Kingdom, Europe and West Airica. In Canada by Texaco Canada
Limited, 90 Wynford Drive, Don Mills, Ontario M3C 1K5, Canada.
-------
E-21
Du Pont Lube OH Additives 564 and 565 are viscous, straw-colored liquids, mildly basic
and completely miscible in all proportions with neutrals and bright stocks. They are insoluble in
water. They are methacrylate polymers of the general structure shown in Figure 1-1, in which ni-
trogen has been incorporated into the molecule. This modification of the methacrylatC; polymers
(good viscosity index improvers and pour point depressants) retains the desirable properties of
these polymers and adds that of detergency and dispersancy.* They are 40% active ingredient
solutions in a light solvent-extracted Mid-Continent neutral oil.
CH3
CHj-
CH3
-C
00
c-o
.1
0
I
C|2 H25
FIGURE 1-1—Molecular Structure of LOA 564 and 565
As shown in Table 1-1, this new type of ashless polymeric detergent—VI improver and
pour point depressant, is available in two versions, LOA 564 and 565. They differ only in the
molecular weight of the active ingredient which affects their relaave effectiveness as viscosity in-
dex improvers and their shear stability, but does not affect their detergent-dispersant properties.
The change in viscosity of these products with temperature is shown in the section on
"Handling."
TABLE 1-1—Typical Physical Properties of LOA 564 and 565
Visco-.ity aJ 210'F, SUS '.
Viscosity of 100'F, SUS
Density, Ibs./gal.
Color, NPA
Poor Point, "F
Flash Point (C.O.C.), °F
Fire Point (C.O.C.), °F
Total Acid No., mg. KOH/g
Tola' Base No., mg. KOH/g
Ash, -Hi. %
LOA 564
1200
9000
7.5
1 —
—10
380
420
0.0
8.0
0.00
IOA 565
3800
29,000
7.5
1—
10
380
420
0.0
8.0
0.00
"A more detailed deicriptioit nf l/ic chemistry cf Ihlt clasa of material and f.s ildergtnry action >nny le found in the pc
"A lYric Cfnsti of Polymeric Difiieraanls for Ilyilrocarlxiii Syttetti?" by C. K. fiixirett, 11'. R. Callin. J. >'. Fronii
/>'. fi'ohf'('».i (ACS. Mtirch 23, IS'i J. Kama* City, Aliisottri) mid "The Control of Low Ttnfitralnre Sludge in Passenger
r Knyinej" by /.'. L. U'ifl/s and £.'. C. JM'.ard (S.-lf, Janiiarj/ It, 13JS, Detroit, Michigan). »•' *
C.
Car
paprrs—
ing and
ran 1
Paxc 1
-------
Effect on Physical Inspections of Motor OH
E-22
LOA 564 and 565 have tittle effect on most of the physical inspection tests normally
made on motor oils as shown by the physical inspection data presented in Table 1-2. Their pres-
ence increases the viscosity (thickening), viscosity index, slightly increases the "base number,"
usually decreases the pour point, and—like all detergents—results in a marked increase in Steam
Emulsion number.
TABLE 1-2—Typica! Effect on Inspection Tests
Base Oil: FurforoJ-ExJracled Mid-Continent SAE 20 (Oil 27)
ADDITIVES
Additive, V/f %
Viscosity a) 210°F, SUS
Viscosity at 1CCTF, SUS
Gravity, "API at 60eF/600F
Color, NPA .
Flash Point (C.O.C.), °F -^- . . . ^^ . -
Fire Point (C.O.C.). CF
Cloud Point, °F
Carbon Residue (Rams.), V/t. % ....
Total Acid No., mg. KOH/g
Tolal Base No nig KOH/g. .....
Ash, V/f. %
Discoloration of Copper Strip
3 Hrs. at 212°F
3 Hrs.'af 300°F
LOA
None
51.5
290
94
28.3
7.37
^ 475
+ 16
5
0.23
0.1
OO
130
0.00
102.8
None
None
564
3.75
59.2
370
112
28.2
7.38
6—
425
465
+16
—35
0.20
0.0
0.1
>1200
0.00
102.2
None
None
LOA
None
51.5
296
91
28.1 •
7.38
6—
420
460
+2
-5
0.26
0.1
O.O
•
255
O.OO
102.2
None
Nona
565
3 75
65 7
432
120
28 1
7 38
6
415
'460
0.4
" —35
0.26
0 1
O 2
•>1200
0 00
102 6
Shear Stability
Shear stability of oils containing VI improvers takes two forms:
A. Temporary shear loss. This is reduced viscosity while the fluid is under mechanical
shear. As soon as the fluid is released from the shearing action, it resumes its original
viscosity. The magnitude of this effect is dependent upon the rate of shear — the
higher the rate of shear the greater the temporary loss.
B. Permanent loss in viscosity etncl VI. This is most probably due to mechanical or oxida-
tivc breakdown of the VI improver molecule, which results in a lower average
molecular weight of the VI improver with consequent loss of thickening and VI
effects. . ,
.' •
Page ? Part 1
-------
E-23
53©©O(Sl[P©[}Ll
D F Kendrick
P O. Drawer 2O3S
Pittsburgh. PA I523O
May 23, 1979
Reference: 5-312LF10
Dr. David Fine
125 Second Avenue
Waltham, Massachusetts
Dear Dr. Fine:
02154
As requested in a telephone conversation with
Mr. Tom Bains of EPA, we have shipped to you via UPS
1-quart samples of each of the following Gulf Motor Oils.
Gulf Super Duty Motor Oil 30 - LS-8645
Gulf Super Duty Motor Oil 15W/40 - LS-8646
Gulflube Motor Oil XHD 30 - LS-8647
Gulflube Motor Oil XHD 10W/30 - LS-8648
If you require any information concerning these
samples, please contact me at the above address or by phone
(412) 665-6241.
Yours very truly,
H. H. Donaldson, Jr.
cc: Mr. Tom Bains - Ann Arbor, Michigan
Gulf
C'L CORPORATION
TELEPHONE 412 / ees-eooo
-------
E-24
Mobil Oil Corporation
P O BOX 1027
PRINCETON. NEW JERSEY 08MC
TECHNICAL SERVICE LABORATI
J
Dr. David Fine
New England Institute
For Life Sciences
125 2nd Avenue
Waltham, Mass. 02154
May 3, 1979
SAMPLE SHIPMENTS
MOBIL DELVAC -1230
MOBIL DELVAC SUPER 15W/40
Dear Mr. Fine:
As requested by Mr. T. Baines of the EPA, we shipped to your
attention via UPS on May 3, 1979, one quart each of Mobil Delvac 123C
and Mobil Delvac Super 15W/40. It is our understanding that these
will be used to determine the contribution of Commercial engine oils
to the emission of nitrosamines. If there are any questions regardir
the samples, please contact these laboratories.
W. A. KENNEDY
NSKotuszenko/dc
cc :
Mr. T. Baines
Environmental Protection Agency
2565 Plymouth Road
Ar.n Arbor, Michigan 48105
-------
E-25
Mcbil Oil Corporation «»ST
* KICULJ vrtOu-
NEW YORK. NEW YORK WOlf
June U, 1979
Mr. Darwin Moon,
Environmental Protection Agency
2565 Plymouth Road
Ann Arbor, Michigan H8105
Dear Mr. Moon:
In response to your telephone inquiry about our engine oil, Mobil Delvac 1,
the Product Data Sheet and "Facts About Synthetic Lubricants" should give you
the information you requested.
The Nitrogen level in new Mobil Delvac 1 is typically about .05^.
•
I have asked that a quart sample be provided to:
Dr. David Fine,
Nev England institute for Life Sciences
125 2nd Avenue
Waltham, Massachusetts 02151*
Very truly yours,
G. R. Jordan
Manager
Marketing Engineering
Division
P. E. S. Department
GRJ:st
Attachment? (2)
-------
E-26
1
Synthetic Fleet Engine Oil
With the increasing emphasis on fuel conservation, Mobil is
continuing to contribute to this effort with the introduction
of a synthetic engine oil branded Mobil Delvac 1. It has been
developed for use in all types of automotive fleet equipment,
including both pn-highway and off-highway equipment hav-
ing either heavy-duty diesel or gasoline engines.
Delvac 1 synthetic engine oil can help because it provides
lower fuel consumption (due to reduced friction), lower lube
oil conTOnTpTionTextenoed oil dram intervals, and longer
filter life. The oil is designed to improve cleanliness and
reduce wear to ensure longer engine life.
The product has outstanding high-temperature stability,
thus ensuring outstanding luLncation under severe engine
loads and at critical ambient temperature applications. Con-
currently, it also provides exceptional low-temperature
fluidity at subzero temperatures that permits faster cranking
and easier starting Delvac 1 is an SAE 30 viscosity oil with
low-temperature fluioity comparat>!e"7o"^in"SAE 5W. to per-
mit proper operation of automotive equipment in extremely
cold weather. Delvac 1 utilizes an optimized combination of
Mobil-manufactured synthetic base stocks to provide this
outstanding wide range of performance characteristics.
Delvac 1 synthetic engine oil meets the performance require-
ments of U.S. military specifications MIL-L-2104C and
MIL-L-46152. It also substantially satisfies the requirements
of MIL-L-46167 specifications for subzero engine oil-
lubrication.
The product exceeds by several-fold key requirements of
API CD/SE and Mack_Diesel C,O-J classifications. Accord-
ingiy, Uelvac 1 has long-term quality retention in terms of
oxidation stability, alkalinity, high-temperature detergency,
dispersancy, protection against corrosion, and sludge pro-
tection, which can permit extended oil drains and longer
filter change intervals.
PRODUCT DESCRIPTION
Delvac 1 synthetic engine oil is a blend of Mobil-produced
'
_oris and caretuiiv-seecieoes>erse
lubricant contams^acarefuny-Dalancea and fiUSIOm-de-
signed additive system which provides outstanding high-
temperature detergency and unsurpassed dispersancy at
both low and high temperatures. The product is highly
resistant to thermal degradation while providing a very high
level of oxidation resistance. These desirable characteristics
are supplemented by a high level of an'iwear and corrosion
inhibitors. Because of its unus.ua! properties. Delvac 1 can
continue to provide satisfactory lubrication without substan-
tial deposits at temperatures up to 100 degrees above the
threshold of operation of conventional mineral oils.
Delvac 1 carries an SAE 30 viscosity rating but behaves
better than a conventional SAE 5W oil at very low tempera-
tures. This is because the viscosity grades of automotive
engine oils are developed according to definitions and test
procedures developed by the Society of Automotive Engi-
neers (SAE) for petroleum lubricants and not synthetic prod-
ucts. Thus, the SAE grade is indicative of fluidity only and
does not define overall quality. As a result, the SAE viscosity
grading system does not truly measure a product's viscosity-
related engine performance. Where a conventional SW oil
does not flow properly at temperatures below 0°F, Delvac 1.
because of the absence of wax crystals, remains fluid at sub-
zero temperatures as low as -50° F.
Delvac 1 has all the advantages of an SAE 30 weight oil with-
out the disadvantage of higher oil consumption inherent in
multigrade oils using very light mineral oil base stocks. This
is because its man-made molecules have higher boiling
points than many of the molecules found in conventional oils.
Delvac 1 does not evaporate as readily in the high-tempera-
ture piston ring area of highly turbocharged diesel engines
at high operating temperatures.
At the high end of the temperature-viscosity scale, 210* F,
Delvac 1 has essentially the same viscosity as most petro^
leum SAE 30 oils. However, because of its higher viscosity
index and its unique molecular structure, it provides a better
protective film than conventional oils over the full range of
operating temperatures encountered.
Delvac 1 exceeds the zinc and phosphorous requirements of
Ford ESE-M2C-144-A specification. International Harvester
Fleet Service Newsletter IHC SLF 76-9. and Chrysler
09-14-77 Technical Service Bulletin. Delvac 1. in addition.
conforms to the Detroit Diesel 7SE 270 (Rev. 10-76) speci-
fication.
TYPICAL CHARACTERISTICS
Typical physical and chemical characteristics of Mobil
Delvac 1 synthetic engine oil are shown in the data sheet
table:
Chanel eristics
¥AE NO.
Gravity, API
Specific Gravity
Pour Point, *F
Flash Point. *F
Viscosity
cp at -40' F (CCS)
cpatO'F (CCS)
cSt at 100' F
cSt at 210*F
cStat300*F
cSt at 400*F
eSt at 40* C
cSt at 100*C
SUS at 10O*F
SUS at 21O'F
Viscosity Index
Sultated Ash. % wt
Total Base Number
Mob* Delvac 1
30
30.7
.8724
Below -65
440
12,500
1.200
62.7
10.3
4.33
2.72
57.3
10.06
291
60.3
164
.98
70
-------
01
E-27
APPLICATIONS
With Deivac 1. because of its unique long-lasting capabilities,
over-the-road fleets, truck rental fleets, truck stops and
owner/operators are able to extend drain intervals up to
IQnjUJQmiles in diesel-powered engines. Deivac 1 was also
Toundto* minimize filter deposits with the potential for
longer filter usage. However, because of variables in filter
quality and service conditions, the optimum filter change
interval should be established in conjunction with the en-
gine and filter manufacturers' guidelines. This should pro-
vide not only savings in maintenance costs and costs of oil,
but also substantial savings in terms of equipment down-
time. Deivac 1 will provide fuel savings of 2.0 to 5.6 percent.
with up to 32 percent savings in oil make-up in over-the-
road service. It can be shown that for a truck operating
100,000 miles per year, the savings in fuel economy, make-
up, maintenance, and down-time will substantially out-
balance the higher cost of lubricant per gallon and provide
a substantial dollar savings per year for the fleet operator.
In pick-up and delivery and utility fleets, particularly gaso- •
line-powered units. 25,000 miles without oil drain is feas-
ible under optimum conditions with Deivac 1. Filter change
intervals can be potentially extended to 25,000 miles or one
year of service if filter quality and service conditions permit.
Under these conditions. Deivac 1 is expected to provide fuel
economy savings comparable to that obtained with diesel
equipment, particularly in stop-and-o.o driving and in cold
weather. Here, Deivac 1 is exoected to provide maximum
benefits in terms of reduced friction. In addition, because of
its low volatility, the product would be expected to provide
a make-up rate below that of conventional oil.
In utility fleets, particularly those that are used to repair
telephone and electric lines in the winter, this type oil has
demonstrated substantial reductions in the cost of batteries
and electrical systems The savings are compounded by sub-
stantial reductions in maintenance and repair expenses by
eliminating road calls to start stalled engines in cold weather.
Also eliminated is the use of high-watt block heaters For
diesel engines, idling time is reduced during periods on the
road
Off-the-road trucks used in the logging and mining indus-
tries under extreme weather conditions would be expected
to benefit from Deivac 1 because of its ability to provide
rapid cold startups and rapid warmups of the engine. Under
these conditions the product provides good pumpability and
good protective oil film which helps minimize wear under
critical operating conditions
In school bus fleets, refrigeration units, small 4-cycle en-
gines, and in diesel service centers and units operating in
Arctic subzero conditions, Deivac 1 should provide excel-
lent low-temperature service — wherever an engine must
operate at subzero temperatures.
In various tests. Deivac 1 generally far exceeded specifica-
tion requirements. For example, in the API CD/SE and Mack
EO-J specifications. Deivac 1 demonstrated its long-term
quality retention characteristics by retaining its high per-
formance level for twice the specified length in a "high-
severity" Mack T-1 performance test. Its oxidation resistance
ability was demonstrated in extended Sequence III C and
CRC L-38 tests. Alkalinity retention was demonstrated in the
extended Mack T-1 test, while high temperature detergency
was illustrated in the "high-severity" Mack T-1 and in the
Mack T-5, and Caterpillar 1-G tests.
Deivac 1 further demonstrated its long-term performance
capabilities in additional tests. For example, copper
-------
E-28
Facts about Synthetic Lubricants
The production of synthetic lubricants starts with syn-
thetic base stocks which are often manufactured from
petroleum. The base fluids are made by chemically com-
bining (synthesizing) low molecular weight compounds
with adequate viscosity for use as lubricants. Unlike
mineral oils, which are a complex mixture of naturally
occurring hydrocarbons, synthetic base fluids are man-
made and tailored to have a controlled molecular
structure with predictable properties.
Synthesized base fluids may be classified as follows:
• Synthesized Hydrocarbons
Olefin Oligomers
Alkylated Aromatics
• Organic Esters
Dibasic Acid Esters
Polyol Esters
• Other
Polyglycols
Phosphate Esters
Silicates
Silicones
Polyphenyl Ethers
Fluorocarbons
• Blends
Mixtures of above
(May also contain minor amounts of mineral oil.)
Six of the base fluids — olefin oligomers, alkylated
aromatics, dibasic acid esters, polyol esters, polyglycols,
phosphate esters — account for more than 90 percent of
the total synthetic lubricants used worldwide. Because
of their importance, these base fluids are detailed in the
remainder of this bulletin.
Synthesized Hydrocarbon Fluids
Mobil's SHF (synthesized hydrocarbon fluids) base
fflOCTWBW^efin ougomcrs synnJesizecTTrornspecific
olcfins by a controlled polymerization process. The re-
sult is a fluid composed of hydrocarbons with a similar
molecular structure.
Since the preferred chemical structures can be selected
and controlled by processing, the synthesized hydro-
carbon fluids are almost entirely paraffinic, giving a
much greater degree of stability than fluids with aroma-
tic or naphthenic ring structures. Also, because unde-
sirable waxy materials are absent, very low pour points
are achieved.
Properly formulated lubricants based on synthesized
hydrocarbon fluids have six noteworthy advantages com-
pared with high quality mineral oil lubricants:
1. Excellent viscosity/temperature properties and shear
stability — provides improved wear protection.
2. Good high temperature oxidation stability —reduces
deposit formation. Typically, the upper operating
limit for SHF lubricants is SO degrees higher on the
Celsius scale (100 degrees on the Fahrenheit scale)
than the maximum temperature for high quality
mineral oils.
3. Good low temperature characteristics (pour point
-55° C [-67° F]) — improves cold weather flow prop-
erties.
4. Compatible with mineral oils — no special system
design required.
5. Long service life — 3 to 5 times better than the best
mineral oils.
6. Low volatility — reduces consumption.
A line of aviation, automotive and industrial lubricants
using SHF base stocks has been developed by Mobil
— many with the registered brand identification of
Mobil SHC as shown in the following table:
Mobil's SHF Lubricants
Mobil Brand
Major Applications
Mobil SHC
Mobil 1
ID resale motor oil
Resale motor oil
Mobil Delvac SHC
Mobil Deivac 1
Mobilube SHC
Commercial engine oil
Commercial engine oil
Arctic gear lube
Mobilgrease 28
Wide temperature grease tor
Industrial use
Mobil SHC 624
Mobil SHC 626
Mobil SHC 629
Mobil SHC 630
Broad temperature industrial
circulation systems & gears
Mobil SHC 634
Mobil SHC 639
High temperature calenders &
worm gears
High temperature calenders
Mobil SHC 824
Mobil SHC 625
Nuclear power plants &
stationary gas turbines
Mobil SHC 1126
High temperature conveyors
The value and performance advantages of these lubri-
cants has been proven and their worldwide availability
is expanding.
Organic Esters
These are cither dibasic acid or polyol types. Dibasic
esters, frequently called diesters, have assets that include
a shear stable viscosity over a wide temperature range
(-75°C to 205°C, -103°F to 401°F), high fita strength
good metal wetting, and low vapor pressure at elevated
-------
JL,
temperatures. Another asset is good additive accepta-
bility enhancing their use in compounded crankcase oils
and in selected commercial lubricants. Mobil markets
diesters in combination with SHF in a number of the
Mobil SHC products. Mobil is currently marketing a
line of diester industrial lubricants for use in rotary
screw and vane compressors and in some reciprocating
types.
Polyol esters, which were developed later than diesters,
have many of the same performance advantages and
extend the service temperature to higher levels. Their
principal use is in aviation turbine oils, such as Mobil
Jet Oil II.
Phosphate Esters
These inorganic esters, used with carefully selected
additives in the Mobil Pyrogard 50 Series, replace
mineral oils where their combustibility may be a
hazard. Pyrogard 50 series provides performance bal-
anced, fire resistant fluids for use in hydraulic and
circulation systems.
The comparative temperature limits of mineral oil and
synthetic based lubricants are shown in the chart below.
Suggested markets for Mobil's synthetic lubricants in
automotive, industrial, and aviation services are item-
ized in the adjacent tabulation. For more complete
product information, please refer to Product Data
Sheets for individual products.
Mobil's Polyglycol Lubricants
Brand
Major Applications
Mobil Glygoyle 11*
Heat transfer systems.
compressors, natural gas valves,
LPG screw compressors and
severe duty bearings and gears
Mobil Glygoyle 22
Mobil Glygoyle 30
Severe duty bearings, gears,
and compressors
Mobil Glygoyle 80
R-12 refrigerant screw
compressors and severe duty
bearings, gears and compressors
'Available in International Division only.
Polyglycols
Polyglycols were one of the first synthetic lubricants.
They are more accurately described by the name poly-
alkylenc glycols and are among the least expensive and
most commonly used synthetic fluids. Primarily, they are
obtained from petroleum and are high molecular weight
polymers of ethylcne or propylene oxides or both. Poly-
glycols have excellent viscosity/temperature properties
and are used in applications from-40°C to 205°C(-40°F
to 401° F) and have low sludge buildup. Mobil branded
polyglycols are shown in the above tabulation.
8
«
•
u.
8
Typical Mineral Oils
SHF
Allcyl Benzenes
Dibasic Acid Esters
Polyol Esters
Polyglycols
Phosphate Esters
u o
• e
0
*
S
U
•
o
1C
CM
O
•
-------
E-30-
Mobil's Synthetic Lubricants — Market/Application
Equipment Type —
Lubricated Unit
Operating
Conditions
Premium Lubricant Recommendations
Mineral OH Synthetic
Advantages of
Synthetic Oils
Industrial
Calender* — Rubber, Plastics,
Board. Tile
Paper Machines — Dryers.
Calenders. Drive Gear Units
Nuclear Power Plants — Vertical
Coolant Motors. 6-9000 hp
Gas Turbines — Small Standby.
Commercial
Steam Turbines — Electro-
Hydraulic Control.
Throitle/Governor
Tenter Frame & High
Temperature Conveyors —
Bearings
Enclosed Gears — Parallel,
Worm. Spur. Bevel
Refrigeration Compressors — SRM
License Screw Compressors
Metal Diecasting Hydraulic
Systems
Mining — Continuous Miners &
Associated Equipment
Primary Metals — Slab.
Continuous Casters. Rolling
Mills. Shears. Laales. Furnace
Controls
Air Compressors
High temperature
180'C to 260'C
(356' F to 500' F)
High temperatures
Annual oil change
8000 hours mm.
Ambient
-SS'C to 60*C
(-65- F to 140' F)
Near superheated
steam lines
1SO'Clo260'C
(302' F to 500' F)
Heavy duty.
shock loaded,
severe service
Severe service
Molten metal,
source ol
ignition
Fire hazards
exist
Fire hazards
exist
Severe service
Mobil D.T.E. AA,
HH. KK
Mobil D.T.E. Ex Hvy,
BB: Mobil Paper
Machine Oils
Mobil D.T.E. Medium
Mobil D.T.E. 797.
Light Medium
Mobil D.T.E. 797.
Light. Mecium.
Heavy Medium
Mobil Etna Oil
No. 6
Mobil Oven
Conveyor Lubricant
Mobilgear 600
Steam Cylinder Oils
Gargoyle Arctic Oil
Scries
Mobil D.T E. 20 Series
Mobil D.T.E. 20
Series
Mobil Pyrogard D
Mobil D.T.E. 20
Series
Mobil Rarus 400.
500 Series
Mobil SHC 634. 639
Mobil Glygoyle 22. 30
Mobil SHC 634
Mobil Glygoyle 22, 30
Mobil SHC 824
Mobil SHC B24, 625
Mobil Pyrogard S3
Mobil Pyrogard 53T"
Mobil SHC 1126
Mobil SHC 600
Series. Mobil
Glygoyle 22, 30
Mobil SHC 626
Gargoyle Arctic
SHC 224. 226
Mobil Glygoyle 11.
22,30.80
Mobil Pyrogard
SO Series
Mobil Pyrogard 53
(Pyrogard D
alternate where
preferred)
Mobil Pyrogard 53
(Pyrogard D
alternate
where preferred)
Mobil Rarus 800
Series
Extended service, reduced deposits.
oxidation and thermal cracking.
Extended service, reduced deposits.
oxidation and thermal cracking.
Extended service, reduced deposits.
Extended service, broader
temperature range ol application,
reduced deposits.
Fire resistant
Reduced deposits and improved
wear protection.
Extended service, better
oxidation resistance at elevated
temperatures.
Improved efficiency.
Fire resistant
Fire resistant
Fire resistant
Extended service, reduced deposits.
Automotive
Passenger Car Gasoline
Engines
Truck & Off Highway Gas
& Diesel Engines
Trucks & Cars. Drive Axles &
Manual Transmissions —
Hypoid. Spiral Bevel &
Spur Gears
Severe start-
stop driving
Arctic or
subzero
Mild to severe
Mobil Super
10W-40
1SW-50
Mobil Oelvac
Special or Mobil
Heavy Duty SWf
Mobilube HD 75W
Mobil 1
Mooil SHC TOW-SO.
15W-SO
Mobil Oelvac SHC'
Mobil Oelvac 1
Mobilube SHC
75W-90
Improved fuel economy, low
temperature starting, oil economy.
and wear protection.
Improved low temperature starting
and operation, longer drain
interval, and fuel and Oil economy.
Improved low temperature starting
and operation, and wear protection.
' Available in International Division only.
tSAE 5W-20.
-------
E-31
Mobil's Synthetic Lubricants — Market/Application (Cont.)
Equipment Typ* —
Lubricated Unit
Operating
Conditions
Premium Lubricant Recommendations
Miner*! Oil
Synthetic
Advantage* ol
Synthetic Dili
Aviation — Military I Commercial
Commercial Turbine Engines — Temperature to
Prult & Whuney. Allison: G E.: 220'C (428"F)
Rolls-Royce Avon. Gnome. Sp«y and
V.per-MIL-L-23699A approved
None
Mobil Jet Oil II
Broad temperature rknge of service.
high temperature stability.
Military Tuoine Engines —
MIL-L-7808H approved
Temperature \0
190'C (374'F)
None
Avrex S Turbo 256 High temperature stability.
Aircratt, All — Wheel Bearings.
Wing Flap Screws — MIL-G-
81322B approved
Temperature
-S5°Cto 180'C
(-67-F to351*F)
None
Mobilgrease 28 Broad temperature range ol
service, high temperature stability.
M©bil Oil Corporation
PRODUCTS DEPARTMENT
15O EAST UNO STREET. NEW YORK. NEW YORK 10017
S£K JQW71KOO
-------
E-32
MAri7 137-
Chevron _, _ , _
Chevron Research Company
A Standard Oil Company of California Subsidiary
576 Standard Avenue, Richmond. California | .-
Mj.l Address P 0 Bo« 16:7. Richmond. CA 94802
f
May 8, 1979
Mr. Thomas M. Baines
U.S. Environmental Protection
Agency
2565 Plymouth Road
Ann Arbor, Michigan 48105
Dear Mr. Baines:
You recently spoke with Mr. K. L. Kipp and Mr. R. 0. Bolt
concerning Chevron engine lubricants suitable for heavy-
duty engines. At your request, we are sending one-quart
samples of the engine oils listed in the attached table
to Dr. David Fine, New England Institute of Life Sciences.
I am enclosing copies of Chevron Teknifaxes which describe
these products in more detail. Please let me know if you
have any further questions.
Very truly yours,
/\j?v csi^£r*-t~f
' R. L. Courtney'f
RLCrccp
Encl. - Table I
Four Chevron Teknifaxes
100 Years Helping to Create the Future
-------
TABLE I
CHEVRON DELO FLEET ENGINE LUBRICANTS
Engine Lubricant
Chevron Delo 100 Motor Oil
SAE Viscosity Grade 10W,
20W-20, 50, 40, 50
Chevron Delo 200 Motor Oil
SAE Viscosity Grade 10W,
20W-20, JO, 403
Chevron Delo 300 Motor Oil
SAE Viscosity Grade 10W,
20W-20, JO, 40
Chevron Delo 400 Motor Oil
SAE Viscosity Grade 10W,
20W-20, JO, 40, 50
Chevron Delo 400
SAE 15W-40
197B
Relative
Sales
Volume1
3.0
1.0
1.3
3.1
0.2
API
Performance
Category
CC
CC,CB,SE,SD
CD
CC,CD,SE,SD
CC, CD, SE
Typical
Compositional Data2
Na,
Wt %
0.03
0.01
0.03
0.17
0.20
Sulfated Ash,
Wt %
o.T't
0.98
1.25
(1.5 for
SAE 10W Only)
0.98
0.98
Zinc,
Wt %
0.1
0.11
0.13
(O.l6 for
SAE 10W only)
0.13
0.13
1Sales relative to Chevron Delo 200 Motor Oil and Chevron Special Motor Oil (all
viscosity grades combined).
2See Chevron Teknifax for additional information.
3Includes Chevron Special Motor Oil volume.
J
CHEYROH RESEARCH
COMPANY
RICHMOND. CALIFORNIA
RLC.
w
I
-------
E-34
Chevron
Delo
100
Motor Oil
(Formerly Chevron RPIVI Delo Special Motor Oil)
o
Description
CHEVRON Delo 100 Motor Oil is a crankcase lubri-
cant developed especially for today's modern diesel
engines. In addition, it gives excellent performance in
those gasoline engines where API Service CO oils are
recommended. It is manufactured from solvent
refined, specially treated, paraffinic base oils having
high viscosity indexes. It is fortified with special
detergent dispersant, oxidation, corrosion, wear
reducing and defoaming additives.
Typical applications
Chevron Delo 100 Motor Oil is specifically designed
for engine services CA, CB, and CC as described by
the API Engine Service Classification System. It
meets the requirements of former specifications
Supplement 1 and MIL-L-2104B.
In addition to its principal use in automotive engines,
this product is widely used in industrial and marine
engines and in hydraulic systems where extreme pres-
sure (E.P.) protection is needed.
Performance qualities
Chevron Delo 100 Motor Oil has been proven in prac-
tically all types of diesel engines, except those requir-
ing a Series 3 Oil, by many years of use in trucks of
all sizes and makes in all parts of the world.
The primary benefits to be obtained from its use are:
#
1. Engine protection — Keeps engines in good con-
dition under severe operating conditions.
2. Oxidation stability — Is inhibited to minimize
breakdown of the oil due to oxidation under the
severe operating conditions of engines, thereby
reducing the harmful effects of the build-up of
sludge and other products of oxidation.
3. Minimizes deposits — Because of effective deter-
gents, dispersants and inhibitors and the natural
resistance to breakdown of the basic oils used,
deposits in engines are minimized. Ring sticking is
kept to a minimum.
4. Minimizes wear — Because of minimum deposits
and effective corrosion inhibition, wear is mini-
mized, thereby extending engine life.
5. Flexibility — Is effective in gasoline engines as well
as in diesel engines.
Qualifications
Chevron Delo 100 Motor Oil meets the requirements
of the following specifications:
— Former Military Specification MIL-L-2104B.
— API Service Classifications CA, CB, CC.
— Detroit Diesel Engine Division's recommendations
for ash and zinc content of oils for their engines.
-------
E-35
Typical test data
SAE GRADES
GRAVITY, °API
VISCOSITY
Poises at 0°F
Kinematic, cSt
at210°F
SSU at 100°F
SSUat210°F
VISCOSITY INDEX
POUR POINT, °F
FLASH, °F
COLOR
I
I
. ASH (SULFATED),WT.%
, /|V:c. WT.%
10W
29.8
17.5
6.1
182
46.2
-20
405
5.0
0.7
0.1
20W-20
28.6
73.0
9.1
363
56.1
-15
445
5.0
0.7
0.1
30
27.6
-
12.4
615
67.9
on 1 1 n
0
470
5.5
0.7
0.1
40
27.2
-
15.5
857
79.9
+10
480
6.0
0.7
0.1
50
26.5
—
20.1
1275
98.5
+ 10
500
3.0
(DILI
0.7
0.1
o
•• I-T.I dota shown :n this table are average values only. Minor variations which do not affect product
.':••.mce are to be expected in normal manufacturing. Please see your Chevron representative for more
•. i.l s.
NOTE:
Chevron Delo 100 Motor Oil
darkens rapidly in use. This is a sign of the high
dispersancy of the oil. It shows the superior ability of
the product to disperse sludge-like materials. It is the
result of the excellent dispersion of sub-micronic
sludge particles, which other oils may allow to
agglomerate and deposit in the engine or filter.
-------
E-36
Chevron
IVlotorOs
o
What type of oils are they?
Chevron Delo 200 Motor Oils are premium quality
automotive crankcase oil: designed for gasoline
engines in severe service and for diesel engines in
moderate to severe duty. Therefore, they are
ideally suited for mixed fleet service.
They are manufactured from 100% solvent refined,
paraffinic base oils, selected for their low carbon-
forming characteristics, high viscosity index and
maximum oxidation stability. To these stocks, a
carefully balanced additive package is added. This
treatment consists of dispersant, detergents, anti-
wear and extreme-pressure agents, oxidation and
corrosion inhibitors and an effective foam
inhibitor.
Where should they be used?
Chevron Delo 200 Motor Oils are recommended
for:
1. Mixed fleets of automotive gasoline and diesel
engines where the manufacturers require oils for
API Services SE or CC. The requirements are
often specified as MIL-L-46152 (SE and CC) or
MIL-L-2104B (CC).
2. Mobile and stationary engines in industrial,
agricultural and marine applications requiring
the use of this type of lubricant.
3. Engines from more than 50 domestic and
foreign manufacturers.
4. Engines which require an oil meeting A.P.I.
service classifications CC and SE.
5. Hydraulic systems where engine oils are
recommended.
How do they perform?
Chevron Delo 200 Motor Oils provide outstanding
control of deposits and wear over a wide range of
operating conditions.
Highly effective additives are selected to enhance
the desirable properties of the quality base oils.
Here is how the finished lubricants do the jobs
assigned to them:
1. High temperature protection against oil
oxidation and thickening. Varnish formation on
pistons, carbon build-up in ring grooves, and
deposits on other engine parts are kept to safe,
low levels,
2. Low temperature protection against sludge
formation. Oil screens, valve train chambers, and
other engine parts are kept cleaner in low
temperature or stop-and-go operation.
3. Rust and corrosion protection against the water
and acids formed by condensation, combustion
by-products or oil oxidation. Bearings and other
engine surfaces are protected by barrier films
and neutralization of metal-eating contaminants.
In fact, running an engine for five minutes on a
fresh charge of Chevron Delo 200 will give
sufficient protection for seasonal tayup.
4. Protection against wear and scuffing. Special
additives guard against piston scuffing and
abnormal wear of parts subjected to extreme
pressures, such as valve train wear points.
5. Improved engine efficiency. Pre-ignition causing
deposits are reduced; positive crankcase
ventilation systems are kept cleaner.
O
•*»!•*••••» »
-------
E-37
0
6. Longer filter life. Most oil-insoluble con-
taminants are kept so finely dispersed by the oil
that they pas's right through the filter medium.
This leaves the filter more time to trap larger,
harmful contaminants. Filter change intervals
are extended accordingly.
Chemically treated filters interfere with the oils
ability to suspend submicronic particles and are
not required.
The immediate darkening of Chevron Delo 200
Motor Oils in use is normal and should be
expected. This is evidence of their superior ability
to disperse contaminants and keep engines clean.
Qualifications met
Chevron Delo 200 Motor Oils meet the specific
requirements of the following:
Diesel Engines—API Service CC
• Aliis-Chalmers—Naturally aspirated engines in
mild duty.
• Caterpillar—Naturally aspirated engines under
reduced drain periods.
• Cummins—Naturally aspirated engines.
• Detroit Diesel—Single viscosity grades only.
• international—Naturally aspirated engines.
• Mack-Naturally aspirated engines (EO-H).
Gasoline Engines—API Service SE
• American Motors
• Chrysler Corporation
• Ford ESE-M2C101-C & ESE-M2C144-A
• General Motors GM 6136-M
Typical test data*
r.AE
' Grade
, 1 0\V
'ZQW 20
30
40
Poises
18°C
•24
57
-
Viscosity cST (SUS)
40°C
44 (205)
71 (330)
116 (538)
160 (740)
100°C
7 (48)
9 (56)
12 (67)
15 (78)
Viscosity
Index
105
100
93
92
Pour
Point
°C
-34
-27
-19
-18
(°F)
(-29)
(-19)
(-5)
(-2)
Flash
Point
°C
207
235
252
254
(°F)
(405)
(455)
(485)
(490)
Sulfated
Ash
Wt. %
0.9
0.9
0.9
0.9
Zinc
Type
Alkyl
Alkyl
Atkyl
Alkyl
Wt. %
0.11
0.11
0.11
0.11
10 change without notice
0
-------
E-38
Chevron
DELO
300
Motor Oil
(Formerly Chevron RPM DELO 300 Motor Oil)
Description
Chevron Delo 300 Motor Oil is a Caterpillar
approved Series 3 Oil. It also satisfies the require-
ments of the former Military Specification MIL-L-
45199B. The product is manufactured from solvent
refined paraffinic base oils having high viscosity
index and low carbon-forming characteristics.
The special detergents and other additives used keep
engine parts clean, particularly in the area of the ring
belt, piston skirt and valve surfaces. As a result they
minimize both low and high temperature deposits and
those ash deposits that cause valve "wheezing" in
certain turbocharged diesel engines. The additives also
help to control the harmful effects in the engine
caused by using high-sulfur fuels.
Chevron Delo 300 Motor Oil contains corrosion
inhibitors which minimize the formation of corro-
sive acids and form protective films on bearings
and all lubricated surfaces. Effective defoaming and
extreme pressure additives are used to satisfy the
requirements of a good hydraulic oil, as well as
providing protection for engines and gear cases.
Typical applications
Chevron Delo 300 Motor Oil was developed
and is recommended for use in diesel engines oper-
ating under very severe service conditions where a
Series 3 Oil is required for £ particular make of
engine. It has also given excellent service in gasoline
engines. This oil is a solution for an operator who
wishes to use a Series 3 Oil in a variety of types and
makes of engines.
It is specifically suited for use in Caterpillar and other
heavy duty engines operated by:
1. Contractors
2. Miners
3. Farmers
4. Truckers
5. Loggers
6. Stationary engine installations
7. Marine installations
It also gives excellent performance in:
1. Hydraulic systems.
2. Gear cases, when motor oil is recommended by the
manufacturer.
3. Engines requiring an oil recommended for API
Service Classification CD.
4. Engines requiring an oil meeting the requirements
of the former Military Specification MIL-L-45199B.
Performance qualities
The performance qualities of Chevron Delo 300
Motor Oil have been proven in laboratory and field
tests. Benefits shown for the new oil include:
Minimizes deposits —
Minimizes ring sticking problems, and controls
deposits in both high and low temperature services.
Minimizes wear —
Contains effective anti-wear agent, neutralizes
acids, and solublizes acidic material to prevent
corrosive wear.
Extends valve life —
Low ash feature controls valve wheezing.
Oxidation stability —
Exceptionally resistant to oxidation.
Rust inhibited —
Protects all metal surfaces under the most difficult
conditions of equipment operation and storage.
-------
E-39
Long oil filter life —
The high dispersancy of the oil assures long life
of oil filters, allowing the oil filter to be more
effective in filtering out abrasive materials.
Engine field tests
Field tests were conducted in over 170 diesel and
gasoline engines in construction equipment and in
more than one million miles of over-the-road heavy
duty trucking.
In addition to extensive testing in all the most
popular makes of diesel engines in contractor-type
service, Chevron Delo 300 Motor Oil was also field
tested and proven in popular make truck engines
selected because they had a high detergent require-
ment and were high output engines. Improvements
were obtained with respect to deposit control,
wear and valve condition with Chevron Delo 300
Motor Oil as compared with a quality conventional
Series 3 reference oil.
To test the ability of Chevron Delo 300 Motor Oil
to solve operational problems including valve
"wheezing'," a field test location was selected
where the operating conditions and equipment
involved were known to present a serious problem.
Units were changed to the low-ash Chevron Delo
300 Motor Oil with outstanding results.
The improvements designed into Chevron Delo 300
Motor Oil add up to many thousands of trouble-
free engine hours (or miles) and low operating
costs.
TYPICAL TEST DATA
SAE GRADE
GRAVITY °API
FLASHPOINT, °F
VISCOSITY
AT 100°F, SUS
AT 100°F, CS
AT 210°F, SUS
AT210°F,CS
VISCOSITY INDFX
POUR POINT, °F
SUL FATED ASH.WT. %
ZINC, WT. %
10W
28.0
395
196
4Z02
47.0
6.35
-25
1.5
.16
20/20W
27.5
440
365
78.75
56.5
9.21
30
27.0
465
590
127.4
68.5
12.56
nc, 1 in
-10
1.2
.13
0
1.2
.13
40
26.5
475
775
167.2
78.5
15.14
+ 10
1.2
.13
o
The test data shown in this table are average values only. Minor variations which do not affect product
performance are to be expected in normal manufacturing. For more details, see your Chevron representative.
NOTE: Chevron Delo 300 Motor Oil darkens rapidly in use as the result of the excellent dispersion of
sub-micronic sludge particles in the oil. This is a sign of the superior ability of the product to disperse sludge
particles which other oils may allow to agglomerate and deposit in the engine or filter.
Package sizes generally available
Chevron Delo 300 Motor Oil is available in: 1-Quart Cans; 5-Gallon Pails; 55-Gallon RSB's.
-------
E-40
Chevron
Delo 400
Motor Oil
Description
When introduced to the marketplace in 1971,
Chevron Delo 400 Motor Oil was the first oil to":
(1) satisfy the full requirements of all major makes
of automotive diesel engines, (2) meet the require-
ments of all domestic brands of gasoline engines,
and (3) meet the requirements of the most recent
military specifications, MIL-L-2104C and
MIL-L-46152.
Subsequent to its introduction, several engine
manufacturers changed their specifications for the
oils to be used in the crankcases of the engines
they build.
In addition, it has become desirable for users to
extend periods between engine oil drains in order
to conserve oil, to reduce environmental problems
and to reduce costs.
The improved Chevron Delo 400 Motor Oil meets
all of the latest requirements of all of the major
automotive engine builders, and allows for extend-
ing intervals between drains.
Chevron Delo 400 Motor Oil contains only alkyl
type zinc dithiophosphates as specified by several
engine builders. This zinc compound provides
excellent anti-wear protection.
Typical Applications
Chevron Delo 400 Motor Oil is a multi-application
oil recommended for use in all major automotive
type diesel and gasoline engines in all types of
service. It is particularly recommended for use in
fleets containing different types of engines made
by several manufacturers.
Qualifications
Chevron Delo 400 Motor Oil meets the warranty
requirements of the following engine
manufacturers:
Diesel Engines
— Caterpillar Tractor Company
— Cummins Engine Company
— Detroit Diesel Allison Division,
General .Victors Corp.
— International Harvester Company
- Mack Trucks, Inc. (EO-H and EO-J)
Gasoline Engines
— American Motors Corp.
— Chrysler Corporation
— Ford Motor Company
(ESE-M2C-144A)
- General Motors Corp.
(Standard 6136M)
— International Harvester
- Mack
- White
Chevron Delo 400 Motor Oil meets the require-
ments of the following API Engine Service
Classifications:
CC, CD, SE
Chevron Delo 400 Motor Oil has been tested in its
most popular grade which meets the requirements
of the following current military specifications:
MIL-L-2104C and MIL-L-46152. It also meets
Allison Type C-? and Vickers hydraulics perform-
ance in Grade SAE TOW.
Field Experience
Chevron Delo 400 Motor Oil is in use in hundreds
of automotive fleets nation-wide. It has given out-
standing performance in trucks and automobiles of
all makes for many thousands of millions of mites
over several years.
Performance Qualities
The performance qualities of Chevron Delo 400
Motor Oil have been proven in laboratory and field
tests. The benefits of this oil include:
-------
E-41
Q
General Use
This one oil can be used in all major automotive
type diesel and gasoline engines in all types of
service. As a result crankcase oil inventory is
minimized and the problem of getting the wrong
oil in an engine is eliminated. It is recommended
for use in transmissions and hydraulic systems
requiring a fluid meeting the Allison Type C-3 in
Grade SAE 10W or Caterpillar TO-2 specification,
SAE 30.
Minimum Deposits
Ash deposits in the combustion chamber area and
on valve surfaces are minimized. Sludge, varnish
and carbonaceous deposits are controlled to extend
engine life.
Minimum Wear
An effective anti-wear agent neutralizes acids and
solubilizes acidic material to reduce corrosive wear
to a minimum.
Extended Drain Intervals
The initial alkalinity (acid neutralizing ability) of
Chevron Delo 400 Motor Oil (9TBN by ASTM
D-2896) is among the highest in motor oils for use
in trucks and automobiles.
Under most operating conditions, drain intervals
can be extended and the oil will still provide excel-
lent protection for the engine parts when Chevron
Delo 400 Motor Oil replaces the more conventional
type universal motor oils.
The optimum oil drain interval can best be deter-
mined by a used oil monitoring system and a good
engine maintenance program.
Oxidation Stability
Exceptionally resistant to oxidation.
Rust Inhibited
Protects metal surfaces under the most difficult
conditions of equipment operation and storage.
Low Temperature and High
Temperature Operation
Provides top performance in engines operating in
both low and high temperature service.
Long Filter Life
The high dispersancy of the oil extends the life of
oil filters, allowing the oil filter to be more effec-
tive in filtering out abrasive materials.
TYPICAL TEST DATA
SAE Viscosity Numbers
Viscosity
At 100°F,SUS
At 100°F,cSt
At210°F, SUS
At210°F, cSt
Flash Point, °F (Mm)
Pour Point, °F
TBN (ASTM-2896)
Sulfated Ash, Wt. %
Zinc, Wt. % (Alkyl)
10W
217
46.5
49.1
7.0
20W-20
328
70.7
55.8
9.0
30
538
116
66.9
12.2
40
757
163
79
15.3
n r i 1 r>
400
-25
9
0.98
0.13
410
-10
9
0.98
0.13
•425
-5
9
0.98
0.13
450
5
9
0.98
0.13
o
NOTE: _ The test data shown in this table are average values only. Minor variations which do not
affect product performance are to be expected in normal manufacturing. For additional
information please see your Chevron representative.
-------
MACK TRUCKS, INC.
One of the Signal Companies (jj
1999 Pennsylvania Avenue, Hagerstown, Maryland 21740
E-42
September 6, 1979
Ar.o Cede (301) 7334300
Ms. Ulku Goff
New England Institute of Life Sciences
125 Second Avenue
Walthatn, MA 02154
Dear Ms. Goff:
Under separate cover we are forwarding new and used
engine oil samples from two different Mack engines,
ETZ675 and ETAZ676, used in highway service. We
understand these samples will be used for an EPA
nitrosamines study.
One pint (four four-ounce plastic containers) of
new oil, used oil at 75 hours, used oil at 150 hours
and used oil at a complete oil change are included for
each engine. Both vehicles are using exactly the same
new oil so only one sample of new oil is included.
Also included are the used oil data with each sample,
and the other data requested are attached.
Should you require additional information please con-
tact me.
Very truly yours,
dk L. T. Murphy7
Project Engineer
Attachment Technical Support Lab
It's part of the language... "BuHt Uke a Mack Truck"
-------
VEHICLE INFORMATION FOR EPA NITROSAMINES STUDY
E-43
MACK UNIT NUMBER
VEHICLE TYPE
MAIN USE
MODEL YEAR
MODEL SIZE
CONFIGURATION
USUAL TRIP LENGTH (MILES)
TOTAL MILES ON VEHICLE
211
212
R685ST
OVER-THE-ROAD
1968
TANDEM AXLE
CONVENTIONAL
3 15 /DAY
681,683
315/DAY
353,959
ENGINE MODEL
DISPLACEMENT
HORSEPOWER
CONFIGURATION
ASPIRATION
TOTAL MILES ON ENGINE
ENGINE MILES AT START OF TEST
MAINTENANCE INTERVAL (MILES)
FUEL USED
OIL BRAND NAME
OIL ADDITIVE
AVERAGE OIL CONSUMPTION (MI/QT)
AVERAGE FUEL CONSUMPTION
ETAZ676 I ETZ675
672 in3
285
235
HIGH TORQUE RISE (MAXIDYNE)
TURBOCHARGE D/ INTERC OOLE D
121,358
121,358
25,000
TURBOCHARGE D
60,174
60.174
16,000
EXXON 260
MOBIL INFILREX 205
EXXON CHEMICAL ECA7320 (.1% NITROGEN)
800
5.4
700
5.4
- A -
-------
E-44
GZDilH
DIESEL (CANADA) LTD
RESEARCH AND DEVELOPMENT DIV
Montreal, May 30th, 1979
Mr. Thomas Baines
Emission Control Technology Division
U.S. Environmental Protection Agency
2565 Plymouth Road '
Ann Arbor, Michigan 48105
Ref.: Diesel_Crankcase_Emissions_Characterization_Prggram_
Dear Tom,
As we confirmed to you in the past, Deutz, in conjunction
with other EMA companies, is interested in participating
in EPA's Diesel Crankcase Emissions Characterization Program.
For that purpose, a total of 4 oil samples (sample volume
= 1 litre each) will be submitted to the New England
Institute of Life Sciences:
Sample No. 1 : Old oil, prior to oil change.
Sample No. 2 : Fresh oil, from drum.
Sample No. 3 : Used oil, with approx. 75 service hours.
Sample No. 4. : Used oil-, with approx. 150 service hours.
Additional information on the samples are given in Attachment
No. 1.
The samples will be obtained from an engine installed in our
field test vehicle.
The following information should contribute to a better evaluat
of the oil analysis results:
!_.__ _Vehicle_Sp_ecifications
Truck: Ford LN 8000 tractor
Weight: 5700 kg
Rear Ratio: 6.14
Trailer: RAM
Length: 8.10 m (27 ft.)
GVKR (truck and trailer): 16 602 kg (36 600 Ibs).
/2
4660 HICKMORE AVE., MONTREAL, QUE., CANADA HAT 1K2 TLX:05-825773 (514)735-441
-------
E-45
^ ___ _
The following are average values:
Service Type: 90% on-highway, 10% city
7 hours per shift
450 - 500 km per shift
The vehicle runs 5 days per week on a 2-shift per day basis
It accumulates approximately 70 hours per week = 5 000 km
(3120 miles) per week.
Engine Type FSL 610
Displacement: 6544 cm3 (400 in3)
Power Output: 160 HP
At Rated Speed: . 3600 min"1
Number of Cylinders/Arrangement: 8-V
Method of Aspiration: Naturally aspirated
Combustion Cycle: 4 stroke, diesel direct
injection
Engine Cooling: Air-cooled
Exhaust Gas Recirculation: No
Crankcase Ventilation: . Open to atmosphere through
an oil separator.
Lube Oil System Capacity (including
oil filter): 14 £ (3.7 US gall.)
The engine belongs to a new engine family development work
done at our Research and Development Centre located in Montreal,
Canada. Since this work is still in progress, the engines are
not yet EPA certified, but covered by EPA's Testing Exemptions
and CARB's Experimental Permits.
The engine was installed in the vehicle in July 1978.
Some engine components were replaced since then (Reasons:
Components re-design, parts failures, etc.).
No engine re-build or major repair has been performed. A
detailed engine inspection was carried out in February 1979,
at which opportunity some components (liners, pistons, etc.)
were cleaned and re-installed.
As of May 21st, 1979, the engine has accumulated a total of
1960 service hours in the vehicle (592 service hours since inspec-
tion in February, 1979) , corresponding to 111 542 km
(69 714 miles) .
/3
-------
E-46
Oil
For a long period of time, all engines at our Research and
Development Centre ran with Rotella T 30 oil supplied by
Shell (Canada) . Approximately 12 months ago, Shell (Canada)
changed the oil denomination to Rotella S 30.
According to Shell, the oil Rotella S 30, available in Canada,
corresponds to Rotella T 30, available in the U.S.A. The
exact differences between these oils, if any, is proprietary
information to Shell, and cannot be released to customers.
Both oil types are classified as SE, CC as per A.P.I.'
requirements.
Shell Rotella S 30 (Canada) has a Nitrogen concentration of
2: 0.21% (mass) .
During the field testing program, oil changes are performed
each 180 - 200 service hours, or approximately each 15 000
km (-9 375 miles) .
6 Oil Con sumtion
The first engines built for the purpose of endurance testing
of major components did not include an optimized liner /piston/
ring package and consequently exhibited high oil consumption.
The field test vehicle is powered by one of these engines.
Its oil consumption level, averaging 6 litres/1000 km
(2.5 US gall./lOOO miles) is several times higher than the
present development engines running in test cells.
7 Fuel
The fuel used by the engine is a commercially available Diese
fuel, bought from Gulf at their service stations.
No additives are added to the fuel by Deutz.
We hope that this information will contribute to your evaluat:
of the oil analysis results. We are looking forward to the
opportunity of sharing your results with us, and the other EMi
members .
Should you need additional historical data in terms of vehicl<
engine usage, please do not hesitate to contact us.
Sincerely yours
DEUTZ DIESEL (CANADA) LIMITED BCC . :
/A Mr. Vossm.eyer
.-? -757"' D, DT, DD , P. Wuensche
E. Sauerteig I /f. • /l AS-TI, AS-TGV
Supervisor f /
Combustion and Emission Development
ES/ghc/D8/Enclosure
-------
A
E-47
ATTACHMENT NO. I
SAMPLE_Noi_l
Oil removed from the engine sump during oil change.
Following parameters apply to this "old" oil:
1. Date of oil change: May 21, 1979
2. Oil type: Shell (Canada) Rotella S 30
3. Total service hours in the sump: 166
4. Total time in the sump: 21 days
5. Distance driven by the vehicle during that time:
11 035 km (6 897 miles)
6. Oil quantity added during that time: 68.5 litres
(18.1 US gal.)
7. Oil consumption during that time: 6.2 fc/1000 km
(2.6 US gal/1000
miles)
New oil refilled to engine sump.
1. Date of refill: May 21, 1979
2. Type of oil: Shell (Canada) Rotella S 30
3. Amount of oil refilled: 14 2, (3.7 US gal.)
4. Oil filter replaced: Yes
Samples No. 1 and 2 were stored in a refrigerator until shipment,
on May 25th, 1979.
SAMPLE_No::_3
At the requested interval, the third sample was collected.
1. Date of sampling: May 30, 1979
2. Oil type: Same as sample no. 2
3. Total service hours in sump: 75.5
4. Total time in sump: 9 days
5. Distance driven by the vehicle during that time:
5 043.7 km (3 152.3 miles)
6. Oil quantity added during that time: 34.6 litres
(9.14 US gal.)
7. Oil consumption during that time: 6.68 2/1000 km
(2.9 US gal./lOOO
miles)
Sample no. 3 was stored in a refrigerator until shipment on
June 4, 1979.
/2
-------
A
E-48
ATTACHMENT NO. i - page 2
Following data applies to the fourth and last sample:
1. Date of sampling: June 7, 1979
2. Oil type: Same as sample no. 2
3. Total service hours in sump: 154.2 litres _^
4. Total time in sump: 18 days
5. Distance driven by the vehicle during that time:
10034.5 km (6271.6 miles) —
6. Oil quantity added during that time:
64.9 litres (17.14 .US gal)
7. Oil consumption during that time:
6.47 V1000 km (2.7 US gal/
/1000 miles)
Sample no. 4 was stored in a refrigerator until shipment on
June 11, 1979.
ES/ghc/D8
04-06-1979
-------
CH
E-49
CATERPILLAR TRACTOR CO.
Pcoria. Illinois 61629
June 19, 1979
Mr. Thomas M. Baines
Characterization & Applications Branch
U.S. Environmental Protection Agency
Ann Arbor, MI 48105
Dear Tom:
Oil Samples for Nitrosamines Evaluation
This letter is to confirm that we are interested in participating in the EPA
diesel crankcase emission characterization program. We look forward to coop-
erating with EPA in this matter but first we would like to see the results of
the MIT evaluation of Dr. Fine's nitrosamine measuring technique.
As you have discussed with R. D. McDowell, the oil samples we will provide are
as indicated by the following table:
Engine
3208 NA
3406 DIT
3406 DITA
Oil Type
AMOCO 300
(15W40)
Chevron RPM
DELO 400
(30W)
Chevron RPM
'4DELO 300
(30W)
Approximate Sampling Schedule
As a Fraction of Change Period
New 1/3 2/3 Drain
New 1/3 2/3 Drain
New 1/3 2/3 Drain
As shown by the chart, you will be receiving four samples from each engine for
a total of 12 samples. The first two engines are operating in trucks owned by
a locally based trucking company. The third engine (3406 DITA) will be operat-
ing in the lab on an on-highway truck cycle dynamometer test. Along with the
oil samples we will supply as much of the requested information as possible. We
shall initiate supplying the oil samples whenever you indicate your contractor
can accept the samples.
If you have any questions or comments, please contact R. D. McDowell or me.
truly yours,
JCHafele
Ph: (309)
sdc
675-5362
ssions Cqntrol Manager
(//Engineering G.O.
-------
F-l
Appendix F
The Results of the Used Oil Samples Acquired by
New England Institute for Life Sciences
-------
F-2
Sample No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Type of Oil
Gulf SOW
Gulf 30W
Chevron Delo
400, SAE30
Mobil Del vac
1200, SAE30
Texaco 30W
Shell 30W
Texaco 30W
Texaco 30 W
Havoline 30W
Gulf 30W
Exxon 30W
Texaco 30W
Texaco 10 W 40
Exxon SAE30 W
Texaco 10 W 40
Gulf 10 W 40
Pennzoil SAE30
Texaco SAE30
Type of Engine
Detroit Diesel 6-71
Detroit Diesel 6-71
Mack Diesel 6-76
Mack Diesel 6-75
MBTA Diesel Bus
Mack 300,
Diesel Maxidine
CMC 366 V-8
CMC 427 V-8 diesel
CMC 351 V-6
? 250 L-6
CMC 366 V-8
CMC 305 Diesel
Chevrole 350 V-8
Gasoline Van
Ford 330
Gasoline Truck
Pick-up Truck
Gasoline
CMC 351 V-6
Gasoline Truck
CMC 379 V-6
CMC 6V53
Miles on Oil
7,000
8,975
6,000
1,400
?
15,000
300
38,972
2,000
4,384
2,584
3,484
2,800
3,000
3,000
600
3,000
DMN (ppl
GC HP!
0.60 O.i
0.95 0.
1.50 1.:
2.50 1.'
0.22 N.l
0.90 l.i
N.D. N.i
Bad Samp
* o.:
* 0.'
* N.l
* 0.'
0.5
38.8 39
2.4
3.1 3.
1.7
19
20
Shell x-100 Hultigrade
Ford Super Premium 10 W 40
Detroit Diesel Truck
Turbo Charged
1980 Ford V-8
Gasoline Car
1979 Ford Mustang
Gasoline Car, in line
-continued-
6,000 9.2
6,700 16.9
2,460 5.2
-------
F-3
Sample No.
21
23
26
28
29
30
31
32
33
Type of Oil
Wolfs Heat + Wolfs Head
20-50W + Quaker State
10 W 30 + Marvel Mystery Oil
Ford 10 W 30 Super Premium
Mobil Special 10 W 30
Oilzum 10 W 40
Cashol 10 W 30
Castrol 10 W 30
Castrol 6TX 20 W 50
Oilzum SE 10 W 40
Conoco Super SAE30
Type of Engine
1967 Chevrole Impala
Gasoline Car, in line
1973 Torino Wagon V-8
Gasoline
1978 Datsun S10
Sports Coupe
Gasoline, in line
1978 VW Diesel Car
Mercedes Benz 2400
Diesel Car, in line
BMW 320i Car
Mercedes Benz 280 SE
Gasoline Car, in line
VW Bus
4 cylinder, opposed
Gasoline
Mercedes Benz 2400
Diesel Car, in line
DMN
Miles on Oil GC
121,000 7.7
1,000 5.6
4,000 9.7
7,991 0.7
51,803 9.2
24,806 19.4
18,282 8.1
1,750 14.2
51,803 9.2
(ppb)
HPLC
6.5
9.5
18.4
14.9
* Could not be analyzed on GC-TEA because of a co-eluting material.
-------
G-l
Appendix G
Nitrosamine Measurements Taken During Method Development Period
-------
G-2
Monthly Progress Report on
CRANKCASE EMISSION CHARACTERIZATION OF DIESEL ENGINES
EPA Contract 68-03-2719
11 September 1978 - 11 November 1978
Submitted by:
Thermo Electron Corporation
101 First Avenue
Waltham, Mass. 02154
Written by:
Approved by:
Ulku Goff
David H. Fine
-------
G-3
Introduction
This report covers the start-up of the contract. Initial attempts have
been made to find an artifact free trapping system for nitrosamine analysis
from crankcase emissions.
Experimental
Sampling was carried out "for 30 minutes at a flow rate of about 1.65
liters per minute (L/M) .. This system that was used for sampling is shown
in Figure J^.
Series A_
4 parallel liquid traps were used. The traps contained the following
collection mediums:
1. 50 ml pH:4 biphthalate buffer solution + 0.5 gm sulfamic acid
+ 0.5 gm L-ascorbic acid.
2. 50 ml pH:4 biphthalate buffer solution + 0.5 pm sulfamic acid
+ 0.5 pm L-ascorbic acid + 1 ppm morpholine.
3. 50 ml IN NaOH solution + 0.5 gm
4. 50 ml IN NaOH solution + 0.5 gm
+ 1 ppm morpholine
The liquid traps were all followed by a Thermosorbtm solid absorbers. These
were use.d so as to determine whether any Nitrosamine escaped from the liquid
traps. Sulfamic acid and L-ascorbic acid were used as nitrosation (by nitrite)
inhibitors. Sodium azide was used to mop up excess nitrogen oxides. Sodium
azide has not been used before in Nitrosamine analysis. Morpholine was added
as a check on the formation of nitrosamines under the sampling conditions.
The presence of Nitroso morpholine would indicate artifact formation in the
traps.
Following collection, 15 ml of the liquid trap contents were loaded
onto Preptubestm and eluted with 60 ml dichloromethane (DCM) into Kuderna-
Danish evaporators. The DCM was evaporated down to about 1 ml in a 55°C
water bath. The sample was then analyzed on both GC and HPLC, using the
TEA as the detector.
The Thermosorb tubes were eluted with 1 ml of 50/50 methanol/DCM mixture,
cleaned on a silica gel column by eluting first with 5 ml pentane, then
with 25 ml DCM. The DCM was evaporated in a water bath and analyzed on GC-TEA.
The Thermosorb tubes could not be used without the silica gel clean up,
because of oil vapors and particulate matter.
-------
G-4
Results
All the traps contained dimethylnitrosamine (DMN) on GC-TEA, which
was also confirmed on HPLC-TEA. The levels are as shown below.
1 - 0.87 yg/m3
2 - 1.03 yg/m3
3 - 0.83 yg/m3
4 - 0.92 yg/m3
The Thermosorb tubes did not have any detectable DMN, indicating that the liquid
traps were retaining all the DMN. Trap 4 also contained N-nitrosomorpholine,
indicating that sodium azide was not a good nitrosation inhibitor. The
Nitrosomorpholine was formed during the collection.
Series B^
Two parallel traps were used, containing the following:
1. 50 ml citrate-phosphate pH:4 buffer + 0.5 gm sulfamic acid 4-
0.5 gm L-ascorbic acid + 0.5 ml butanol-2 +1.6 ppm diethylamine
(80 yg). The length of connecting line was 6.5 ft.
2. As above with the length of the connecting line being 1 ft.
During this run different lengths of connecting tubing were used for
trap 1 and 2, to check for possible artifactual formation of DMN in the
transfer line.
The liquid traps were followed by Thermosorbtm solid absorbers.
The contents of the liquid traps were extracted in a separatory funnel
with 3 x 20 ml DCM. DCM was evaporated at 55 C in a Kuderna-Danish evaporator
down to 1 ml, and then analyzed on GC-TEA.
Results
DMN levels as follows:
1-0.85 yg/m3
2-1.1 yg/m3
The Thermosorb washes did not contain any detectable nitrosamines.
Formation of DEN was not observed.
The trap solution was checked for the presence of diethylamine (DBA)
at the end of the sampling. Analysis showed the presence of 20 yg DEA
in the trapping solution. This DEN was not formed, even though adequate
-------
G-5
precursor amine was still present in the trap. As a control, fresh Citrate
-phosphate pH:4 buffer was analyzed for nitrosamines. No detectable background
nitrosamines were found to be present in the buffer solution.
Apparatus Used
The GC analysis was made with Thermo Electron GC-661 interfaced to
Thermal Energy Analyzer -(TEA-502).
HPLC analysis was made using Varian 8500 pumps interfaced to TEA-502/LC.
GC-column - 10% carbowax + 0.5% KOH chromasorb WHP. 80/100. Carrier gas
Argon, 20 ml/min. Column temperature 125 - 150°C.
HPLC column - Lichrosorb Si60, (10 y) . Solvent - 80/10/5 isooctane/DCM/
acetone.
Bendix Mesa C-115 type air pumps were used for sample collection. The
flow rate of the pumps was calibrated against a mass flowmeter (Hastings).
Summary
The formation of N-morpholine with KOH trapping system, might be occuring
during the concentration step of the organic solvent. That possibility is
eliminated with pH:4 buffer system, because the amines are not extracted
out of the acidic solutions with organic solvent.
Future Work
Nitrosamine levels will be measured in the presence of high levels
of added NO^ dimethylamine gas, and NO and dimethylamine present at the
same time.
Measurements will also be made at different engine load and speed levels.
NO measurements on the crankcase emissions will also be made.
A
-------
f •
FIGURE 1. System for Collection of Nitrosamines from Crankcase emissions.
-------
G-7
Monthly Progress Report on
CRANKCASE EMISSION CHARACTERIZATION OF DIESEL ENGINES
EPA Contract 68-03-2719
November II - December 22, 1978
Submitted by
Thermo Electron Corporation
101 First Avenue
Waltham, Mass. 02154
Written By: Ulku Goff
Approved By: David Fine
-------
G-8
Introduction
This report covers the period between November II through December
22,.1978. During this period, liquid traps containing citrate-phosphate
buffer and thermosorbs were examined.
Experimental
Analytical Apparatus Used'
The GC analysis of liquid trap samples were made with Thermo
Electron GC-661 interfaced to a Thermal Energy Analyzer (TEA-502). The GC
column contained \Q% Carbowax + 0.5% KOH chromosorb WHP 80/100. Carrier
gas, argon, 20 ml/min, column temperature I25°C. The GC analysis of
Thermosorb samples were made withShimadzu GC 6 AM interfaced to a Thermal
Energy Analyzer-502. GC column contained 5% PEG Chromosorb WAW, 60/80,
carrier gas argon, 50 ml/min. Temperature programming was used between 90
-I20°C at a rate of IO°C/min.
Bendix Mesa C-115 type air pumps were used for sample collection.
The flow rates of the pumps were calibrated against a ma.'s flow meter
(Hastings).
Engine Conditions
Light load
OiI temperature: 80°C
Blowby temperature: 49°C
Engine Speed: I800 RPM
Load: 100 ft. Ib
Med t urn Load
OiI temperature: 82°C
Blowby temperature: 70°C
Engine Speed: I800 RPM
Load: 400 ft. Ib.
-------
G-9
Heavy Load
OiI temperature: 84°C
Blowby temperature: 68°C
Engine Speed: 1800 RPM
Load: 600 ft. Ib.
Series C - Engine Load;High - Two parallel liquid traps contained
the following collection medium:
I. 50 ml pH:4, citrate-phosphate buffer + 0.7 gm L-ascorbic acid +•
,0.7 gm sulfamic acid + I ml butanol-2 + 1.6 ppm diethylamine (80 pg).
2. 50 ml pH:4, citrate-phosphate buffer + 1.6 ppm diethylamine
(DEA). In this run, a mixture of 3 ppm NOX was bled into the system
before the liquid traps. A moisture trap, consisting of a 200 ml conical
flask was used before each pump.
Following the 1/2 hour collection period, the liquid trap contents
were loaded on Preptubes™ and eluted with 60 ml dichloromethane (OCM) Into
Kuderna Danish evaporators. The DCM was evaporated down to about I ml in
a 55°C water bath. The samples were analyzed on GC, using TEA as the
detector.
Results and Conclusions
The traps contained the following amounts of dimethyinitrosamine
(NDMA): I) I.01 yg/m3 and 2) I.II pg/m3. No diethyInitrosamine was
observed indicating that the method was not susceptible to an NOX
artefact at an NOX level of 3 ppm.
-------
G-10
Series D - In this run, ThermoSorbs™/N Air Sampler were tried as the collection
medium. They contain a solid absorber to trap nitrosaraines. Two background
samples were taken at the air intake point of the engine. Following a two-hour
collection period, the ThermoSorbs™/N Air Sampler were eluted with 1 ml,
(collected volume), 10/90 methanol/dichloromethane mixture. The samples were
analyzed on GC using TEA as the detector. No detectable volatile nitrosamines
were observed.
Series E - Engine Load: High
4 parallel ThermoSorbs were used. They were treated as follows:
1. Plain ThermoSorb
2. Plain ThermoSorb
3. 25 yg of morpholine was injected just before the ThermoSorb
4. 100 ppm NO + 3 ppm NC>2 was bled in just before the ThermoSorb
Following a 1 hour collection period, the ThermoSorbs were eluted with 5 ml
pentane (collected volume), dried by a N2 gas stream prior to elution with 1
ml 10/90 methanol dichloromethane mixture. The samples were analyzed on GC
using TEA as the detector.
Results and Conclusions
The samples contained the following amounts of NDMA:
1. 1.0 yg/m3
2. 1.4 yg/m3
3. Sample was lost
4. 0.9 yg/m3
We conclude that 100 ppm NO and 3 ppm N02 do not cause an artifact in the NDMA
analysis.
Series F - Engine Load: Medium
Two parallel ThermoSorbs were used and treated as above.
-------
G-ll
Results
Thermosorbs contained the following amounts of NDMA;
I. 2.8 yg/m3
2. 2.I yg/m3
Series G - Engine Load;Light
Two parallei Thermosorbs were used. One of the Thermosorbs could
not be analyzed due to the contaminated nature of the sample.
Results and Conclusions
I. 0.6 yg/m3.
The correlation between load, NOX levels and nitrosamine levels will be
examined.
The engine was not available between November 15 and December 18,
1978.
Summary
The samples collected on Thermosorb showed a great deal more
compounds as compared to liquid traps, which might cause problems during
mass spectral analysis.
Future Work
The nature of the unknown compounds will be briefly examined En
order to determine whether any of them are indeed N-nitrosamines. An
evaluation of liquid traps and Thermosorbs will be made. It will be
decided as to which traps to use for collection of samples that are
required for mass spectral analysis.
-------
G-12
Monthly Progress Report on
CRANKCASE EMISSION CHARACTERIZATION OF DIESEL ENGINES
EPA Contract 68-03-2719
December 22, 1978 through January 22, 1979
Submitted by:
New England Institute for Life
Sciences
125 Second Avenue
Waltham, MA 02154
Written by:
Approved by:
Ulku Goff
David Fine
-------
G-13
Introduction;
This report covers the period between December 22, 1978 through January 22,
1979
Experimental;
Analytical Apparatus Used:
The GC analyses were made with a Thermo Electron GC-661 interfaced to
a TEA-502. The GC column contained 5% PEG Chromasorb WAW, 60/80. The
carrier gas flow was 50 ml/min. For NDMA analyses, temperature
programming from 90°C to 120°C, at a rate of 10°C/min was used. N-nitroso
morpholine (NMOR) and N-nitrosopyroI idine (NPYR) analyses were carried out
at a GC temperature of 170°C.
The HPLC analyses were made with a Varian 8500 LC pump interfaced to a
TEA-502. The LC columns were Lichrosorb SI 60 lOu (3.2 mm x 250 mm) and
Lichrosorb NH2, (3.2 mm x 250 mm) and were supplied by Altex Scientific,
Inc. The solvent systems were 4/17/79 Acetone/DCM/isooctane, and 10/90
DCM/isooctane respectively.
Bendix Mesa type C-115 air pumps were used for sample collection. The
flow rates of the pumps were calibrated against a Hastings mass flow
meter.
Samples (31-40)
Engine Conditions;
Load; 600 ft Ibs
Engine speed: 1800 rpm
OiI temperature: 85°C
Blowby temperature: 63°C
Hours on the engine: 230-240
*
Hours on the oil: 90-100
Engine Oil: Chevron Delo 400, SAE 30
-------
Samples (41-44)
Engine Conditions;-
G-14
Load: 300-700 ft Ibs
Engine Speed: 1QOO rpm
OiI temperature: 83-87°C
Blowby temperature: 57-70°C
Procedure:
Hours on the engine: 251-255
Hours on the oil: 6-10
Engine Oil: Mobil Del vac 1200,
SAE 30
The sampling of the crankcase exhaust was accomplished using pairs
of parallel traps and the results are shown in Table I and Table II.
Following the 1 hr sampling period, the contents of the liquid traps
were extracted in separatory funnel with 3 x 15ml dichIoromethane
(DCM). DCM was poured through 15 gms of sodium suIfate into the
Kuderna-Danish (K.D.) evaporator.Sodiurn sulfate was washed with 5 ml of
DCM. The samples were evaporated down to about 2 ml in a 55°C water bath
and were analyzed by GC and HPLC, using TEA as the detector.
One ml samples of traps #41, 42 and 43 were drawn out prior to
extraction and nitrosated to check for the presence of pyrolidlne or any
other amine that might be present in the traps. The results are given in
Table III.
Results and Discussion:
The results are given in Table I and Table It. Traps #31 and 32 were
spiked with 25 ug of morpholine (mor) as a check for the artifactual
formation of N-MOR in the traps. These traps showed the presence of
*
n-mor. As other traps (33-36; 39-40) were analyzed, the N-MOR levels were
found to be very close to levels in traps #31 and 32. For this reason
N-MOR was assumed to be present in the crankcase emissions at about 0.9
ug/rrp level.
-------
G-15
In traps #37 and 38, where MOR was injected into the sampling line
just prior to the traps, N-MOR levels were higher. The formation of
N-MOR was about \.5% and indicating that the formation of nitrosamlnes was
possible in the lines at 25 ug amine level.
In traps #41-44, NDMA levels were higher and the presence of
N-MOR was not .observed. The reason for this higher result is not clear,
but the fact that the engine was operating with a fresh engine oil of a
type different from previous sample runs may have had some influence, and
suggests that a correlation between nitrosamine level and the age of the
oil might require investigation.
In trap #43, the presence of N-PYR was not observed, indicating that
the traps were artifact-free under the sampling conditions. When one ml of
the above trap solution was nitrosated, N-PYR was formed indicating that,
at the end of sampling, pyrolidine was still remaining in the traps,
available for nitrosation.
In Table HI, nitrosated samples show the presence of DMA and
MOR, indicating that the nitrosamine precursors were present in the
crankcase emissions. Engine fuel or the oil itself might be the source of
the possible nitrosamine contamination. A preliminary analysis of engine
fuel by GC-TEA showed the presence of 18 ppb NDMA concentration.
The analytical results of samples collected on Thermosorb™ tubes were
not conclusive due to contamination of the nitrosamines with co-eluting
materials. Since a clean-up procedure would mean extended analysis time
and lowered recoveries, the liquid traps were preferred for the analysis.
None of the above results were corrected for recoveries.
Combined samples (traps 33, 34, 35, 36, 39, 40) and sample #44 were
sent for mass-spectral analysis.
-------
G-16
Cone I us ion:
The engine crankcase emission contained NDMA at levels varying from
3.1 ug/rrv^ (average) to 11.9 ug/m^ (average) and N-MOR from
non-detectable to 0.9 ug/m-^ (average) depending on oil.
Mass-spectrometric confirmation is underway.
Expend itures:
As of January '4, 1979, $25,144 was spent, bringing the balance to
$67,449.
-------
G-17
Table I. Nitrosamine levels in crankcase emissions, using engine oil:
Chevron Delo 400, SAE 30.
Trap # Solution NDMA (ug/m3) N-MOR (ug/m3 )
31 . 40 ml, PH:4 Citrate-Phos 3.1 1.1
Buffer + 25 ug morp.
32 40 ml, PH:4 Citrate-Phos 3.0 1.2
Buffer + 25 ug morp.
+ 1 ml Butanol-2 + 0.5 gm
Ascorbic A.
33 40ml, PH:4 Citrate-Phos 3.1 0.4
Buffer + 1 ml Butanol-2 +
0.5 gm Ascorbic A.
34 • 40 ml, PH:4 Citrate-Phos 2.8 0.9
Buffer
35 40 ml, PH:4 Citrate-Phos 2.6 0.7
Buffer
36 40 ml, PH:4 Citrate-Phos 2.8 1.1
Buffer
37 40 ml, PH:4 Citrate-Phos 3.5 6.4
Buffer + 25 ug morpholine
injected into the line
+ 0.5 gm Ascorbic A + 1 ml
Butanol
38 40ml, PH:4 Citrate-Phos 3.3 5.2.
Buffer + 25 ug morpholine
injected into the line
39 40 ml, PH:4 Citrate-Phos. 3.4 0.9
Buffer + 1 ml Butanol-2
+ 0.5 gm Ascorbic A
40. 40ml, PH:4 Citrte-Phos. 3.5 1.1
Buffer
-------
G-18
Table II. Nitrosamine levels in crankcase emissions, using engine oil:
Mobil Delv'ac 1200, SAE 30
Trap
Solution
NDMA (yg/m )
N-MOR (yg/m ) N-PYR(yg/i
G.C. HPLC
41 40 yl,pH: 4 citrate-
phos buffer 12.6 11.5
42 40 yl,pH: 4 citrate-
phos buffer 11.4 10.0
43 40 yl,pH: 4 citrate-
phos buffer
+ 50 yg pyrolidine 11.1 11.3
44 40 yl,pH:4 citrate-
phos buffer 12.5 11.9
N D
N D
N D
N D
N D
-------
G-19
Table III. Trap Contents that had been nitrosated
Trap NDMA DMA (after N-MOR MOR (after N-PYR (after
nitrosation) nitrosation) nltrosation)
41
42
43
12.6 yg/m3
11.4 yg/m3
11-1 yg/tn3
44 ng/ml
76 ng/ml
53 ng/ml
ND
ND
ND
11.5 ng/ml
11.0 ng/ml
ND
ND
122 ng/ml
(spike)
-------
G-20
Monthly Progress Report on
CRANKCASE EMISSION CHARACTERIZATION OF DIESEL ENGINES
EPA Contract 68-03-2719
January 22, 1979 through February 22, 1979
Submitted by:
New England Institute for Life Sciences
125 Second Avenue
Waltham, Mass. 02154
Written by:
Approved by:
Ulku Goff
David H. Fine
-------
G-21
Introduction:
' This report covers the period between January 22 through February
22, 1979. During this period, some artifact and blank experiments were
carried out in relation to crankcase emission analysis. Confirmatory
tests were performed on NDMA found in emissions.
A method was developed for oil analysis and 11 oil samples were
analyzed on GC-TEA and HPLC-TEA.
Experimental;
Analytical Apparatus Used:
The GC analyses were made with a Thermo Electron GC-661 interfaced
to TEA-502. The GC columns contained 5% PEG Chromasorb WAW, 60/80 and
10% Carbowax 20M +0.5% KOH on Chromosorb WHP, 80/100. NDMA analyses were
carried out at 120 C, N-pyr and N-MOR analyses were carried at 170 C.
The HPLC analyses were made with Varian 8500 LC pump interfaced to
a TEA-502. The LC columns were yPorasil lOy (3.9 mm x 300 mm) .and Lichrosorb
Si60, 10y (3.2 mm x 250 mm). The solvent systems were 5/95 acetone-isooctane
and 7/93 acetone/isooctane respectively.
Crankcase Emission Samples (45-46)
Engines Conditions;
Load: 160-600 ft Ibs
Engine speed: 1800 rpm
Oil temperature: 82-88°C
Blowby temperature: 69-71 C
Hours on the engine: 268
Hours on the oil: 23
Engine oil: Mobil
Delvac 1200, SAE 30
-------
G-22
Procedure;
The sampling and analysis of crankcase exhaust was done as explained
in the previous report, but the sampling period was reduced to 1/2 hour.
The results are given in Table 1.
One ml samples of the traps #45 and 46 were drawn out prior to extrac-
tion and nitrosated to check for the presence of amines. The results are
given in Table II.
pH:4 citrate-phosphate buffer blank and pH:4 buffer + NO blank experi-
A
ments were carried out according to the procedures below:
pH:4 citrate-phosphate buffer blank experiment;
40 ml of the buffer solution was kept at 35° C (temperature above engine)
in water bath and air was pulled through it for 1 hour. Trap contents were
treated as the real samples.
pH;4 citrata-phosphate buffer + NO blank experiment:
1 1 x c
40 ml of the buffer solution was kept in 35°C water bath. While 2.2
1 / min air was pulled through the buffer solution, <09 ppm NO + 7.7 ppm
N0~ were bled in for 1 hour. Trap contents were analyzed as the real samples.
Confirmatory Tests;
Samples #45 and 46 were combined and cleaned on aluminum oxide (II-III).
The presence of NDMA was confirmed by the following tests.
1) HPLC
2) The combined sample was spiked with NDEA and irradiated with UV
for 1 hour and analyzed on GC-TEA
-------
G-23
• 3) The combined sample was spiked with NDEA and treated with glacial
acetic icid for 1 hour and analyzed on GC-TEA.
Oil and Fuel Analysis;
#2 fuel oil was obtained from the fuel tank of Mack diesel 675. 30 ml
of the fuel was spiked with NDEA at 95.3 ppb level and extracted with 2x5
ml 25% MeoH in H?0 in a separatory funnel. MeoH/ILO layer was poured into
a Preptube and extracted with 50 ml DCM. DCM was reduced to 1 ml in 55°C
water bath. The results are given in Table III and IV. Oil samples were
obtained from local auto dealers and service stations and were analyzed
by bubbling air for 1 hour through a 50 ml oil sample which had been heated
to 110 C. 0.5 gm ascorbic acid, dissolved in 1 ml water and 3 drops of
a-tocopherol were added into oil as nitrosation inhibitors (Fig. I).
Nitrosamines were collected on Thermosorb tubes and were eluted with 1 ml
Methanol. The Thermosorb tubes and oil were shown to be artifact free by
spiking with an amine and looking for the formation of corresponding nitros-
amines. The air used, was checked for the presence of nitrosating agents by
placing a morpholine spiked Thermosorb at the air inlet of the flask. There
was no formation of N-MOR. The results of the oil analyses are given in
Tables III and IV.
Nitrosation of Mobil Delvac 1200, SAE30;
A 50 ml sample of the above metioned oil was placed in a 500 ml flask
and a mixture of air + NO (100 ppm NO + 7 ppm N09) was bubbled through the
X /L
-------
G-24
oil at 110°C for 1 hour. Nitrosamines were collected on Thermosorb and
eluted with 1 ml Methanol. The results are given in Table III.
Results and Discussion;
In trap #46, the presence of N-pyr was not observed. This indicates
that the traps were artifact free even at high NO levels. The agreement
X
of the NDMA levels in both traps indicates the same thing.
When trap contents were nitrosated, they showed the presence of N-pyr
indicating that pyr was remaining in the traps, available for nitrosation
during the sampling. Formation of high quantities of NDMA indicated the
presence of DMA in the crankcase emissions. The blank experiments showed
no detectable amounts of nitrosamines with or without the presence of NO .
x
The complete destruction of the NDMA-TEA signal by UV irradiation and
no change of signal with treatment by glacial acetic acid points to a pure
NDMA signal.
Conclusion:
Amounts of NDMA in the oil samples varied from non-detectable levels
to 2.5 ppb. When a sample of Mobil Delvac 1200, SAE30 was nitrosated by NO ,
X
the NDMA level was raised to 11.5 ppb indicating that the nitrosatable pre-
cursers of NDMA exist in the oil sample and can be nitrosated by NO . So it
x
appears, then, that the oil used is a very likely source of nitrosamines in
the emissions.
-------
G-25
Table 1
Nitrosamine Levels in Crankcase Emissions, Using Engine Oil:
Mobil Delvac 1200 SAE30
Trap No. Solution NDMA (yg/m3) N-pyr (ng/ml)
45 40 ml, pH:4 Citrate-phosphate
Buffer + 62.8 yg pyrrolidine 8.4 N.D.
46 40 ml, pH:4 Citrate-phosphate
Buffer + 62.8 yg pyrrolidine +
215 ppm NO + 15.3 ppm N02 9.0 N.D.
-------
G-26
TABLE II. Trap Contents that had been Nitrosated
Trap # -DMA PYR
45 14.5 ng/ml 182.5 ng/ml (spike)
46 40.0 ng/ml 254.1 ng/ml (spike)
-------
G-27
TAB^E III. Oil and Fuel Analysis
1.
2.
3.
4.
5.
6.
7.
8. -
9.
10.
11.
12.
13.
Type of Oil
Gulf 30W
Gulf- SOW
Chevron Delo
400, SAE30
Mobil Del vac
1200, SAE30
Texaco SOW
Shell 30W
Texaco SOW
Texaco 30W
Havoline SOW
Gulf SOW
Exxon 30W
Texaco SOW
#2 Fuel Oil
Type of Engine Miles on the Oil DMN (ppb) DMN
GC HPLC after
Nitrosation
Detroit Diesel 6-71
Detroit Diesel 6-71
Mack Diesel 6-76
Mack Diesel 6-75
MBTA Diesel Bus
Mack 300, Diesel
Maxidine
CMC 366 V-8
CMC 427 V-8
Diesel
CMC 351 V-6
? 250 L-6
CMC 366 V-8
CMC 305 Diesel
7000
8975
6000
1400
7
15,000
300
38,972
2000
4384
2584
3484
0.60 0.60
0.95 0.70
1.50 1.30
2.50 1.90 11.5
0.22 N.D.
0.90 1.0
N.D. N.D.
- Bad Sample -
* 0.54
* 0.40
* N.D.
* 0.48
9.0 3.0
* Could not be analyzed on GC-TEA, because of a co-eluting material
-------
G-28
TABLE IV. Oil and Fuel Nitrosamine Recoveries and
Detection Limits
Oils Recoveries (%) Detection Limit (ppb)
0.1
0.2
0.7
2.5
0.8
0.8
0.8
DMN
DEN
DPN
DBN
N-pip
N-pyr
N-Mor
80
73
40
7
23
29
29
Fuel Oil DEN 75 0.5
-------
H-l
Appendix H
Diesel Tailpipe Exhaust Analysis for Nitrosamines
-------
H-2
While at SWRI, we ran three tests on Mack Diesel exhaust using pH4
phosphate-citrate buffer traps as the collection medium. The extraction of
nitrosamines from the traps were carried out as described in Section III, TASK
I. The results are described below.
Fuel: National Average #2 (Sulfur Content: 0.235% by weight).
Engine: Mack ETAY (B) 673A
Mode Oil NDMA (ug/m3) NDMA (yg/min)
5 Amoco 300 SAE30 0.8 13.4
3-4 Mobil Delvac Super 15 W 40 0.3 N.D.
2 Mobil Delvac Super 15 W 40 1.1 13.8
N.D. - Not Determined
-------
1-1
Appendix I
Nitrogen Content of Some of the Oils
-------
1-2
Nitrosated (ppb)
Type of Oil Nitrogen Content % NDMA NMOR
Arco fleet plus S-3 15 W 40
Arco fleet plus S-3 30 W
Chevron Delo 400 15 W 40
Chevron Delo 400 30 W
Chevron Delo 300 30 W
Chevron Delo 100 30 W
Exxon HD X Plus 30 W
Exxon HD-3
Exxon HD-3
Gulf Super Duty Motor Oil 30 W
Gulf Lub Motor Oil XHD 30 W
Gulf Super Duty Motor Oil 15 W 40
Gulf Lub Motor Oil XHD 10 W 30
Gulf Lub XHD 30 W
Mobil Delvac 1200 30 W
Mobil Delvac Super 15 W 40
Shell Rotella 15 W 40
Shell Rotella 30 W
Valvoline HD Super HPD 30 W
Valvoline All-fleet 30 W
Valvoline All-fleet 15 W 40
0.1
0.1
0.2
0.17
0.01
0.03
0.08
0.1
0.11
0.048
0.013
0.056
0.013
0.013
0.04
0.05
0.13
0.13
0.025
0.02
0.022
2.0
4.8
5.4
N.D.
1.0
0.5
1.0
1.3
0.8
1.3
0.7
15.0
39.0
1.0
2.4
N.D.
1.6
0.8
3.3
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
7.7
1.0
1.4
5.6
N.D.
N.D.
N.D.
*r = -0.06
*r2 = 3.7 x 10-3
*Excluding the Mobil Data:
*r = 0.51
*r2 = 0.26
*r (correlation coefficient), was obtained from the least-squares linear
regression analysis of the two variables, namely, nitrogen content of the oil
and NDMA content of the nitrosated oil.
-------
J-i
Appendix J
Background on Nitrosamin.es
-------
J-2
BACKGROUND ON NITROSAMINES
I. INTRODUCTION
The interest in N-nitroso compounds (N-nitrosamines) began following the
observation in animals of the toxic and carcinogenic effects of N-nitroso-
dimethylamine (NDMA) (Barnes, J.M. and Magee, P.N., 1954; Magee, P.N. and
Barnes, J.M., 1956).
The first report of their toxic effect on humans was a report by Freund,
H.A. (1937) who described the hepatotoxic effect of NDMA after autopsy findings
of two chemists indicated that they have been accidentally poisoned by this
compound. Since these findings, several N-nitroso compounds have been
extensively investigated for their carcinogenicity by Druckrey et^ al^ (1967) and
reviewed by Magee and Barnes (1967). More recent reviews of their toxicity
(Magee, P.N.; Swann, P.F., 1969), carcinogenicity and metabolism (Magee, P.N. et
al, 1976), and mutagenicity (Montesano, R. and Bartsch, H., 1976; Neale, S.,
1976) are also available. What these studies have demonstrated are that many of
these compounds are potent carcinogens that have a high degree of specificity in
inducing tumors in various species and among target organs within the same
species. Over 100 of the approximately 130 different N-nitroso compounds tested
proved to be carcinogenic in these studies and in a variety of animal species.
For example, N-nitrosodiethylamine (NDEA) has been tested in at least 14
different animal species and none were found dependent upon the structure of the
N-nitroso compound and the route of administration in the test animal. Dose
response studies using NDMA and NDEA with less than 100 rats have indicated that
doses as low as 1-5 ppm of these compounds in the diets are marginally
carcinogenic. While many of these N-nitroso compounds have been demonstrated to
-------
J-3
be potent animal carcinogens, their carcinogenic risk to man (the probability
that defined exposures to these chemicals will lead to or increase incidence of
cancer in man) has not yet been assessed.
In order to address the topic of the possible carcinogenic hazard that
N-nitroso compounds may pose for humans, it is necessary to locate sufficient
populations of exposed people to determine these effects. However, until such
epidemiological assessments can be made, it must be assumed, on the basis of the
many animal studies, that humans will not be uniquely resistant to their
carcinogenic action. Indeed if human populations are found that have excessive
(higher than justifiable) exposure to these compound, prompt action should be
taken to eliminate or reduce their exposure. Since cancer produced from
carcinogenic compounds is a delayed toxic effect and since animal studies show
dose related responses to these agents it would be prudent to assume (until
evidence can be obtained) that any exposure to the carcinogenic N-nitrosamines
constitute a risk.
Until as recently as 1975 most of the interest in the environmental
occurrence of N-nitroso compounds centered around their occurrence in nitrite
preserved foods such as cheese products, fish, and fish meal and biological
samples and in in vivo formation from precursor chemicals. With the discovery
of NDMA in the atmosphere of an urban area in Baltimore, Maryland (Fine, D.H.
et al, 1976), near a facility manufacuring 1,1-dimethylhydrazine (a rocket fuel)
from NDMA and in the air near a large producer of dimethylamine in Charlestown,
West Virginia, the environmental emphasis on these compounds began to shift.
Further discoveries of N-nitroso compounds in products and environments such as
cosmetics (Fan, T.Y. et al, 1977a), tobacco and tobacco smoke (Hofmann, D., et al
-------
J-4
1976), indoor atmospheres under conditions of excessive tobacco smoking
(Brunnemann, K.D. and Hoffmann, D., 1978), in the air of a factory producing
dimethylamine (Bretschneider, K. and Matz, D., 1976), in synthetic cutting
fluids (Fan, T.Y. et al, 1977; Rappe, C. and Zingmark, P.A., 1977) and in some
widely used herbicides (Ross, R. et al, 1977), have further shifted the emphasis
of the environmental search for human exposure to these compounds. It is now
apparent that any situation where the precursors of these compounds (amines and
nitrosating agents) may exist together that there is a high likelihood of
finding N-nitroso compounds. Considerable evidence exists that indicate the
nitrosation reactions (those reactions that result in the production of
N-nitroso compounds from precursor amines and nitrosating agents) can occur in
soils, organic waste or water in areas where industrial or other waste
discharges contain large amounts of amines (Ayanaba, A. et al, 1973).
N-nitrosamines are the nitrosated derivative of secondary amines with the
Rl\
general formula ^Jt-NO, R^ and R2 being virtually any organic group. One
R2
of the simplest members of this family of compounds is N-nitrosodimethylamine
CHi\
N-NO. This compound is a regulated carcinogen under part 1910 of the
CH3"""
Occupational Safety and Health Standard. N-nitrosamines may be formed by the
reaction of secondary amines and nitrous oxides. However, under some conditions
primary and tertiary amines can also be nitrosated to produce these compounds
(Smith, O.A.S. and Loeppky, K.N., 1967; Wartheson, J.J. et al, 1975). The NO,
or nitrosyl part of the compound, can be derived from nitrogen oxides such as
NO, N02» ^0^ or ^2^3 Or from nitrous acid or nitrite salts.
N-nitrosamines can also be formed by transnitrosation whereby other nitro or
nitroso compounds serve as the amine nitrosating agent (Buglass, A.J. et al,
-------
J-5
1974; Singer, S.S. et al, 1978; Fan, T.Y. et al, 1978).
In view of the many possible synthetic pathways for the formation of
N-^nitrosamines, human exposure to these compounds is a virtual certainty. Such
exposure is most likely to occur if the precursors exist together in materials
having human contact (e.g. foods, air, drugs, cosmetics, drinking water, etc.)
or if such materials already contain pre-formed nitrosamines. In fact, the list
of items that have now been demonstrated to contain measurable levels of
preformed N-nitroso compounds has grown considerably over the past decade. Many
secondary amines such as dimethylamine, diethylamine and morpholine are produced
in large quantities for industrial and consumer use. Products produced from
these amines are, for example, used in agricultural chemicals, detergents, rust
inhibitors, rubber additives, solvents, drugs, plastics, leather tanning,
textiles, cosmetics, synthetic cutting and grinding fluids, etc (Mitre Technical
Report, 1976). Of particular interest to this work is the fact that many of the
oil additives that are commonly used in crankcase oils contain amines or amine
generating compounds. Given the wide spread use of amines and the ubiquitous
presence of nitrous oxides both in the air and, especially, in crankcase
atmospheres, the likelihood of N-nitrosamines being found in these products is
high.
II. CHEMISTRY
The preparation of N-nitroso compounds in the laboratory has traditionally
involved the reaction between a secondary amine and sodium nitrite under acidic
conditions (Boyer, J.H., 1969; Fridman, A.L. et al, 1971). This amine
nitrosation reaction has been studied in considerable detail by a number of
investigators, and has been extended to include reactions with various amine
-------
J-6
derivatives such as amides, ureas, guanidines, carbamates, peptides,
nucleosides, lactams, etc. The kinetics and mechanism of the reaction with
nitrite under acidic conditions has been discussed (Fridman, A.L. et al, 1971;
Mirvish, S.S., 1977). Not only can secondary amines undergo nitrosation by
nitrite, but it has long been known that tertiary amines can also partake in
this reaction (Fridman, A.L. et al, 1971). Most recently, Tannenbaum et al
(1978) have demonstrated the formation of N-nitrosamines from primary amines and
nitrite, as well as catalytic effects by inorganic thiocyanate. The overall
yields for these types of reactions, in the absence of a catalyst, are generally
low (0.1-0.5%). A general review of the reactions of primary amines with
nitrous acid is available (Scanlan, R.A., 1975), and possible reaction pathways
have been proposed (Wartheson, J.J. et al, 1975).
N-nitrosation reactions are generally slow at neutral or alkaline pH due
to low equilibrium concentration of the active nitrosating intermediate, nitrous
anhydride (^03). However, an appreciable nitrosation rate for secondary
amines can occur at pH 6-11 in the presence of suitable catalysts such as
chloral or formaldehyde (Roller, P.P. and Reefer, L.K., 1974). Keefer has also
shown that various metal ions can catalyze these reactions under basic
conditions (Keefer, L.K., 1976). N-nitrosamine formation has also been shown to
be accelerated by certain micro-organisms at acidic pH (Archer, M.C. et al,
1978) . Still other catalysts have been recently elucidated with regard to the
basic nitrous acid reaction (Davies, R. et al, 1978). Inhibition of the nitrous
acid nitrosation reaction has been shown with a wide variety of inorganic and
organic compounds, such as ascorbic acid, sulfamic acid, tocopherol, and others
(Fan, T.Y. et al, 1977; Mirvish, S.S., 1975; Groenen, P.J., 1977; Mergens, W.J.
-------
J-7
et al, 1978: Archer, M.C. et al, 1975; Douglass, M.L. et al, 1978).
Tertiary atnine type compounds also undergo the nitrosation reaction with
nitrous acid, and this subject has been extensively reviewed (Boyer, J.H., 1969;
Mirvish, S.S., 1975; Hein, G.E., 1963). Although most tertiary amines possess
low rates of nitrosation under the usual reaction conditions, examples have been
shown to undergo a rather rapid formation of N-nitrosamines (Lijinsky, W. et al,
1973; Eisenbrand, G. et al, 1979). A detailed study of the mechanisms of
nitrosation of tertiary amines by nitrous acid has recently been presented by
Ohshima and Kawabata (1978). They also discuss the formation of N-nitrosamines
from two tertiary amine oxides.
For many years, it was assumed that the most important system for
nitrosation of amines was nitrous acid (or nitrous anhydride, ^03). It is
now apparent that several other routes are available for the efficient
conversion of amines to their N-nitroso derivatives. Thus, Challis and
Kyrtopoulos have demonstrated that under oxygen rich conditions, nitric oxide
itself can nitrosate both primary and secondary amines in organic solvents
(Challis, B.C. et al, 1978). However, under these conditions, nitric oxide
itself is a poor nitrosating agent, and presumably it is the oxidation product,
nitrogen dioxide and subsequent products, that are the effective nitrosating
agents. Challis et al, have also demonstrated a catalytic effect on the
reaction with nitric oxides by inorganic metal salts and molecular iodine
(Challis, B.C. et al, 1978). Some of the salts effective in these reactions
were those of zinc, copper, iron, and silver, but the most effective catalyst
was 12- These metal salts catalyzed reactions in organic solvents are
considerably faster in the rate of N-nitrosamine formation than comparable
-------
J-8
reactions with nitrous acid.
It has been .mown for many years that certain oxides of nitrogen, viz.,
^03 (nitrous anhydride) and ^0^ (dinitrogen tetroxide) can readily
nitrosate amines and amine derivatives (Fridman, A.L. et al, 1971; Challis, B.C.
et al, 1978). However, it has only been recently demonstrated that both primary
and secondary amines react in neutral and alkaline aqueous media (pH 7-14) to
form the corresponding N-nitrosamines (Challis, B.C. et al, 1978). The
mechanism of nitrosation by complex nitrogen oxides have been discussed by
Challis and Kyrtopoulos (1979).
Another route for the formation of N-nitrosamines involves a reaction
termed transnitrosation, whereby the nitrosyl group of a N-nitrosamine may be
transferred to a secondary amine. Thus, in the case of N-nitrosodiphenylamine
and morpholine, under the appropriate solvent and temperature conditions, it is
possible to generate N-nitrosomorpholine and diphenylamine. Transnitrosation
involving N-nitrosamines have been extensively studied by Buglass et al (1974)
and more recently by Singer et al (1978). Transnitrosation by aromatic
N-nitroso derivatives appears to be rapid under elevated thermal conditions in
nonpolar, organic solvents, polar solvents, and under aqueous acidic conditions.
It is possible that transnitrosation can also occur from other nitrosyl donor
compounds, such as C-nitroso, S-nitroso, etc. The nitrosation reactions by
organic nitrite (0-NO) have been known for some time, and constitute one of the
established methods for the preparation of N-nitrosamines (Boyer, J.H., 1969;
Fridman, A.L., 1971). This may be considered a transnitrosation reaction, since
it involves the transfer of the nitrosyl group from a donor molecule (0-NO) to
an acceptor molecule, the secondary amine. The mechanism of nitrosation by
-------
J-9
organic nitrites (-0-NO) may also involve the intermediacy of nitric oxide,
which is then oxidized to nitrogen dioxide. Thus, the mechanism may involve the
intermediate dinitrogen tetraxide (^0^) as the active nitrosating species
(Challis, B.C. et al, 1978).
Nitrosation of amines by aliphatic C-nitro compounds has been known for
the past fifty years (Fridman, A.L. et al, 1971). Tetranitromethane for example
effectively nitrosates amines to form the corresponding N-nitrosamines. This
type of reaction has recently been studied in greater depth by Fan, T.Y. et al,
both with regard to the generality of the reaction and its application to other
amines. It would seem that many aliphatic C-nitro and aromatic C-nitro
compounds can nitrosate secondary amines, as well as tertiary amines, to varying
extents.
From a synthetic point of view, there are many other methods for the
preparation of N-nitrosamines in the laboratory. They may involve the use of
nitrosyl halides, nitrosonium tetrafluoroborate, and other nitrosyl donor
reagents (Boyer, J.H, 1969; Fridman, A.L. et al, 1971). However, in general,
these methods for the formation of N-nitrosamines are not as widely employed as
those previously mentioned.
III. ANALYTICAL METHODS
In order to successfully determine the extent of N-nitrosamines in the
crankcase emissions at the part-per-billion (yg/nr*) or the part-per-trillion
(ng/m-5) level, it is essential to have analytical techniques that are
sensitive, selective and free of false results. Without a sensitive and
selective detection method, screening for N-nitroso compounds would be both
-------
J-10
costly and time consuming.
The analtyical system used in this study employed both gas chromatography
and high pressure liquid chromatography with detection by a TEA analyzer (Krull,
I.S. et al, 1978). The TEA analyzer is specifically designed for the detection
of N-nitroso compounds at the part-per-trillion (ppt) level. False positive or
false negative findings of N-nitroso compounds, can arise from either the
creation or loss of these compounds due to the analytical method employed in
sampling, sample preparation or detection. This problem of false results can
arise in analytical determination of any compound. However, in the case of
N-nitroso compounds the problem of false results is further aggravated by the
multitude of reactant and reaction conditions that can give rise to these
compounds (Krull, I.S. et al, 1978). Furthermore, some of these compounds are
relatively unstable and/or volatile and losses during the sample work-up or
analysis can result.
In choosing the methods for screening crankcase emissions for
N-nitrosamines we were mindful of those factors that may adversely effect the
analysis. N-nitrosamines are relatively easy to make and are also fairly
labile. They are sensitive to prolonged thermal treatment, as well as
photochemical degradation (Polo, J. and Chow, Y.L., 1976; Doerr, R.C. and
Fiddler, W., 1977). In addition, certain N-nitroso derivatives are not stable
to excessive conditions of pH, and beta-hydroxynitrosamines undergo degradation
under alkaline conditions (Loeppky, R.N. and Christiansen, R., 1978). Most, if
not all, N-nitroso derivatives undergo reactions with inorganic acids, and this
has formed the basis for the denitrosation of such compounds (Downes, M.Y. et
al, 1976). The acids active in denitrosation of N-nitrosamines are halogen
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J-ll
acids, such as HC1, HBr, and HI (Eizember, R.F. et al, 1978). With regard to
photochemical reactivity, Fiddler, et al (1978) have shown that most volatile
N-nitrosamines, and presumably nonvolatile ones also, are rapidly destroyed by
the action of ultraviolet light.
One of the most significant physical properties of N-nitroso derivatives
is the relative ease of dissociation of the N-NO bond. For example, in
N-nitrosodiphenylamine, the energy required to break the C-N bond is 105
kcal/mole, whereas the bond dissociation energy for the N-NO bond is only 11
kcal/mole. For simple dialkylnitrosamines, the energy required for the N-NO
bond dissociation is on the order of 40-60 kcal/mole. This relatively low
energy requirement for release of nitric oxide from N-nitrosamines means that
exposure of N-nitroso compounds to temperatures of (400-500*C), can be a
selective method for the removal of nitric oxide. It is this physical property
of N-nitrosamines that allowed for the successful development of the TEA1"
analyzer (Krull, I.S. et al, 1978).
TEA™ ANALYZER
In 1973, Fine and Rufeh proposed the use of chemiluminescence to detect
N-nitrosamines via the formation of the nitrosyl radical, after thermal cleavage
of the N-NO bond (Fine, D.H and Rufeh, F., 1974). This system has been
successfully developed by Fine et al (1975). A gas chromatograph, operated
isothermally or with temperature programming, can be interfaced to the TEA
analyzer (Fine, D.H. and Rounbehler, D.P., 1976; Castegnaro, M. and Walker,
E.A. , 1978; Havery, D.C. et al, 1978).
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J-12
GAS CHROMATOGRAPHY - TEA™ ANALYZER
This system operates by having gaseous samples exiting the GC swept
through a catalytic pyrolyzer by the GC carrier gas, usually argon. All
N-nitroso compounds present in the sample entering the pyrolyzer are cleaved at
the N-NO bond, thereby releasing the nitrosyl racical (NO). The yield of NO is
approximately stoichiometric for most N-nitrosamnes. Solvent vapor, pyrolysis
products, and NO pass through a cold trap at -150°C which, in principle, removes
all materials other than the permanent gases. The NO and the carrier gas are
then swept into a low-pressure reaction chamber, where the NO reacts with ozone
to generate electronically excited singlet state nitrogen dioxide (N02*). The
key reactions occurring in the reaction chamber are:
R2
NO
Pyrolysis ,
350-550°C R N R + N°
NO* - ^ N02 + light
The excited N02* then decays back to its ground state with the
concomitant emission of light near the infra-red region of the spectrum (0.6 -
2.8y). The intensity of the light emitted is a direct measure of the amount of
N-nitroso compound present in the sample. The TEA analyzer system is selective
because it produces a response only if a compound meets several requirements.
Thus, pyrolysis must occur within a few seconds within the catalytic pyrolysis
tube at a moderate temperature, to give a product which survives a cold trap,
and reactions with ozone at reduced pressure. The product of this reaction must
then emit light in the near infra-red region of the spectrum. The
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J-13
chemiluminescent reactions must be sufficiently rapid for the emission to occur
before the reactants leave the reaction chamber. Because of the relative
selectivty of the TEA analyzer, it is possible to analyze N-nitroso compounds
quantitatively at high sensitivity, even in the presence of many co-eluting
compounds. This reduces the clean-up procedures for samples prior to the GC-TEA
step. The detection limit in GC-TEA is routinely less than 100 pg
(10~12g) for NDMA or NPYR.
It should be mentioned that the TEA analyzer is not totally specific for
N-nitrosamines alone (Stephany, R. and Schuller, P.L., 1977; Lafleur, A. et al,
1978). Thus, several other classes of organic compounds will also respond to
the TEA analyzer, to varying molar extents, depending on the structure of such
compounds. Organic nitrites (0-NO), N-nitrosamines (N-IK^), C-nitroso (C-NO),
poly C-nitro (C-N02), nitrates (0-N02) and inorganic nitrite may produce
responses to the TEA analyzer. It is also probable that other classes of
organic compounds, e.g., S-nitroso and S-nitro will also be found to respond on
the TEA analyzer. Thus, the presence of a response by GC-TEA for a new sample
can not necessarily be taken as proof of the presence of an N-nitroso compound.
Confirmation of positive results is necessary, either by the use of chemical
tests and/or by the use of high resolution mass spectrometry. There is strong
evidence that high resolution mass spectrometry with continuous peak matching is
a reliable confirmatory technique for the identification of N-nitrosamines
(Gough, T.A. et al, 1977).
Various applications of GC-TEA for the determination of volatile N-
nitrosamines have been reported in the literature. Collaborative studies
conducted by the luternational Agency for Research on Cancer (IARC) employing
-------
J-14
widely differing analytical methods in different laboratories have been reported
(Castegnaro, M. and Walker, E.A., 1978; Havery, D.C. et al, 1978). Both
qualitatively and quantitatively, there was good agreement with the "correct"
(spiked) value by both GC-TEA and high resolution mass spectrometry with
continuous peak matching. The TEA analyzer has two major advantages over other
detectors for N-nitroso compounds. It is generally up to 100 times more
sensitive than alternative, routine GC detectors such as mass spectrometry and
flame ionization or alkali flame ionization types. Also, the TEA analyzer is
more selective for the N-nitroso moiety than other detectors. This selectivity,
with the reservations already mentioned, allows the TEA analyzer to be used as
maximum sensitivity, even for the most complex and crude samples. Such a
feature allows for only minimal sample clean-up and pre-concentration prior to
analysis. This greatly reduces the possibility for artifact formation and/or
loss.
GAS CHROMATOGRAPHY - MASS SPECTROMETRY
Mass Spectrometry (MS) combined with gas chromatography has customarily
been used for the analyis of GC amenable N-nitrosamines. The spectral
fragmentation patterns of many N-nitrosamines have been documented, and several
papers detail the fragmentation pathways for a number of N-nitroso compounds
(Gough, T.A. and Webb, K.S., 1973; Dooley, C.J. et al, 1973). Gadbois, D.F. et
al (1975) and Gaffield, W. et al (1976) have presented information on chemical
ionization mass spectrometry. Mass spectrometric techniques for the analysis of
volatile N-nitrosamines have been reviewed recently by Gough, T.A. (1978).
It has been observed by Gough and Webb (1973) and Dooley et al ( 1973, that
-------
J-15
even with high resolution, a potentially interfering fragment
with a retention time close to that of NDMA may be encountered. A resolution of
70,000 is required for complete separation, and a mismatch between the two
compounds can be observed even at a resolution of 7,000. Other potentially
undesirable effects have been observed by Gough et al (1977) and may arise from
the method of displaying the high resolution signal. Under certain conditions,
co-eluted materials on the GC may suppress the mass spectrometer response and
hence effect quant?tation (Stephany, R.W., 1977). This, and other problems,
can be overcome by the use of a peak matching technique. Here, the mass region
in the vicinity of the reference fragment (usually derived from a fluorinated
hydrocarbon) and the N-nitrosamine fragment of the same approximate mass are
alternatively scanned every few seconds. The method allows for the observance
of the reference peak as well as the rise and fall of the N-nitrosamine peak.
Monitoring only the precise mass of the parent N-nitrosamine ion using high
resolution mass spectrometry can lead to erroneous results (Gough, T.A. et al,
1977). One of the most reliable procedures for identifying N-nitrosamines is by
mass spectrometry, using selective ion monitoring and continuous peak matching
with high resolution, after initial GC separation (Gough, T.A. et al, 1977;
Gough T.A., 1978). Low resolution mass spectrometers are less costly and more
widely available, *nd they can be used successfully on relatively clean
extracts, particularly for compounds having long GC retention times and complex
fragmentation patterns. It should be noted that parent ion monitoring at high
resolution with peak matching requires considerable operator skill. Also, not
all commercially available multi-ion monitoring units are suitable for use at
high resolution, and they cannot normally be used with a wide mass range without
-------
J-16
a loss of sensitivity at the higher mass region.
HIGH PRESSURE LIQUID CHROMATOGRAPHY - TEA™ ANALYZER
The TEA analyzer, when operated in the HPLC mode operates on the same
basic principles as discussed above with regard to GC-TEA. However, here a
liquid sample is swept through the catalytical pyrolyzer by argon carrier gas,
and all organic materials are quickly vaporized and/or pyrolyzed. Following the
pyrolyzer, the solvents are condensed out inside large (300 ml) vacuum cold
traps, prior to entering the chemiluminescent chamber.
At the low temperatures used in the cold traps, only the carrier gas, the
nitrosyl radical (TO), and a very few, low molecular weight organic species pass
through both cold traps. The remaining TEA operations are identical to those
already described for the GC-TEA mode.
With the HPLC-TEA, screening procedures for background N-nitroso compounds
can proceed relatively rapidly, and a large number of samples can be studied in
a short period of time. Exhaustive extraction of environmental or industrial
products, followed by HPLC-TEA determinations, allows for the rapid
establishment of upper limits of background N-nitroso compound levels. With
HPLC-TEA, the limits of detection for most N-nitrosamines are in the range of
0.1 - 1.0 ng, per injection. This allows for a sensitivity range of
approximately 10-100 ppb for most compounds, but this depends upon the
particular sample preparation and chromatographic conditions employed in any
given analysis.
IV. ARTIFACTS (false positive and negative results)
The problem with false negatives are more managable and less of a concern
-------
J-17
than is the problem of false positives. False negatives can arise from loss of
sample from the traps during collection, sample exposure to UV or sunlight, or
by acid degradation of the collected N-nitrosamines. Internal analytical
controls using an added known N-nitrosamine will reveal any tendacy of the
chosen analytical method to degrade the N-nitrosamines. As yet there is no
evidence that indicates the false negatives are a major problem with the
analytical methods used in this study. A large number of laboratory and field
studies have demonstrated that airborne nitrosamines are completely trapped in
our system. Photo degradation is minimized by either protecting the sample by
light exclusion or by avoiding strong light sources when the samples are taken.
A major source of false positives are either cross contamination or
artifact formation of N-nitrosamines during the trapping or sample work-up
steps. Another problem lies in the area of TEA detected unknown compounds,
i.e., compounds for which we have no standards that match the observed
chromatographic elution time. This problem of artifacts in the analysis for
N-nitrosamines has been reviewed recently by Krull, I.S. et al (1978) and control
of contamination has been extensively discussed by Zief, M. and Mitchell, J.W.
(1976).
Because the detection techniques used in this study are highly specific
for only those compounds which can release the nitrosyl moiety, the overall
problem of contamination is limited to those compounds. However, when
performing routine analysis in the ppm-ppb range, the problem of contamination
is still relevant. To control for contamination, negative blanks are regularly
used. These blanks include every step used in the analysis, including the same
batches of chromatographic materials and chemicals, except the sample.
False positives are most frequently caused by the inadvertant formation
-------
J-18
during the sample collection, work-up or analysis of precisely those materials
which one is analyzing for. If a N-nitroso compound is found to be present in
an entirely new sample, serious consideration must be given to the possibility
of a false positive. For example, Angeles, R.M. et al (1978), have recently
described the artifactual formation of various N-nitrosamines during extraction
of environmental samples. They have shown that inorganic nitrite is solid phase
can serve as a nitrosating agent for solutions of organic amines in non-aqueous
solvents (CH2C12, CH2ClBr, CH2Br2, etc.). Logsdon, D.J. et al (1977)
have also recently reported on the artifactual formation of N-nitrosamines
during the analysis of water samples for organic matter.
A simple precaution to minimize the possibility of artifact formation is
to use the bare minimum of analytical steps. This approach is feasible with the
GC-TEA and HPLG-TEA methods of N-nitroso analysis, provided that the sample(s) are
in a form suitable for direct introduction into the apparatus. For example,
Ross.R. et al (1977) have directly introduced aqueous pesticide formulations
into both GC-TEA and HPLC-TEA in order to show that NDMA was present in the
formulation itself. In the case of cutting fluids, Fan, T.Y. et al (1977b)
introduced crude formulations of up to 40% triethanolaaiine and 18% sodium
nitrite directly into HPLC-TEA in order to confirm the presence of NDE1A.
If a particular sample cannot be introducted directly into the TEA, it
should be extracted and worked up with as few analytical operations as possible.
In the case of air samples, Fine, D.H. et al (1977) were able to directly
analyze by GC-TEA, materials isolated using cryogenic trapping, without any
extraction or concentration. Thus, the possibility of artifactual formation was
limited to method of sampling and/or the chromatographic or detector conditions
-------
J-19
employed.
The source of the nitrosating agent which could be responsible for a
positive artifact has included nitrite contamination of the sample itself (Fan,
T.Y. et al, 1977; Fine, D.H., 1978), open column chromatography on nitrite
contaminated packing materials for GC and LC columns (Eisenbrand, G. and
Spiegelhalder, B., 1977), use of too high an injection port temperature in GC
analysis of a complex sample (Fan, T.Y. and Fine, D.H., 1978), absorption of
nitrogen oxides from ambient air (Eisenbrand, G. et al, in press), N-nitrosamine
contaminated deionized water (Gough, T.A. et al, 1977; Fiddler, W. et al, 1977)
and organic solvents (Eisenbrand, G. et al, 1978). The most frequent source of
the amine precursors is the sample itself. In order to determine if all or part
of the N-nitroso compounds present are a result of the analytical methods, a
number of experiments are arranged so that they yield maximum information with a
minimum of time and effort.
The first such experiment is the addition of readily nitrosatable amine,
together with a nitrosating agent (inorganic nitrite and/or oxides of nitrogen)
to the original sample. Usually, there are several possible candidates for the
amine precursor and nitrosation agent. This is then followed by the same
sequence of analytical steps as for the analysis itself. If there is an
increase found in the amount of N-nitroso compound(s) present, then artifact
formation may have occurred. Two additional precursor control experiments then
become necessary. Excess amine(s) is then added to the sample, without any
added nitrosating agent, and the amount of N-nitroso derivative determined. If
additional N-nitroso compounds are observed, then it is likely that artifact
formation has occurred. If no increased formation of N-nitroso material is
-------
1-20
observed, then a third experiment is carried out with added nitrosating agent
alone, in the absence of added amine(s). If additional N-nitroso compounds are
not formed, then it can be reasonably assumed that there was no artifact
formation in the original analysis. If, on the other hand, enhancement is
observed, then artifact formation may have occurred. If artifact formation has
indeed occurred, then the analytical method must be modified to avoid this.
In order to reduce the number of precursor experiments required, initial
work should be done with rather high concentrations of amine(s) and nitrosating
agent or amine (nitrosating agent) alone. The amounts of precursors added to
the sample in these initial experiments should be from 10 to 100 times the
amount of N-nitroso compound determined originally. If, with these large
concentrations, enhancement is not observed, then there is no need to use lower
precursor concentrations. However, if high concentrations lead to enhancement,
further experiments are needed to progressively lower concentrations.
In the case of air monitoring and crankcase emission sampling, where
nitrogen oxides are always present, collection of samples in unsuitable traps
creates additional routes for artifact formation of N-nitroso compounds
(Challis, B.C. et si, 1978). Validation procedures for air sampling have been
described (Fine, D.H. et al, 1977). If the addition of the precursor amine does
not lead to enhancement, then positive artifact formation of the N-nitroso
compound is probably absent. The use of deuterated amine precursors has been
used to resolve the question of artifact formation in air sampling (Fine, D.H.
et al, 1977).
-------
J-21
USE OF ADDED INHIBITORS
Several workers routinely add nitrosation inhibitors such as ascorbate
(Hecht, S.S. et al, 1974), or sulfamic acid (Fan, T.Y. et al, 1977a) to all
samples prior to analysis. Nitrosation inhibitors are effective, because at the
proper pH they compete with amines for available nitrite (Mirvish, S.S., 1975a;
Mirvish, S.S., 1975b). Care is required to ensure that the inhibitor is added
in excess so as to account for the available nitrite. If addition of an
inhibitor decreases the amount of N-nitroso compound which is observed, it is
probable that some or all of the N-nitroso material originally determined was
due to artifact formation.
ARTIFACT FORMATION VIA TRANSNITROSATION
Artifact fornation due to transnitrosation within the sample can be
detected by use of control experiments similar to those already discussed.
Also, the use of combined GC-TEA and HPLC-TEA can usually eliminate the
possibility of artifact formation due to transnitrosation, if this occurs during
the chromatographic process itself (Fan, T.Y. and Fine, D.H., 1978). Often a
temperature above ambient is required to produce a significant transnitrosation.
Thus, by working room temperature, as is done with most HPLC, this problem can
usually be entirely prevented.
False positives are known in gas chromatography (Fan, T.Y. and Fine, D.H.,
1978; Umbreit, G.R., 1977) and to a lesser extent in HPLC (Eisenbrand, G. and
Spiegelhalder, B., 1977; Freed, O.J. and Mujsce, A.M., 1977). The formation of
a N-nitroso material on-column during HPLC on nitrite-free packing is unlikely.
If a N-nitroso material is shown to be present using a variety of HPLC columns
-------
J-22
and conditions, it is strongly indicative that no positive artifact formation
has occurred during HPLC. For volatile N-nitrosamines, a combination of GC and
HPLC techniques has been used to eliminate positive artifact formation during
chromatograph (Ross, R. et al, 1977; Fine, D.H. et al, 1977; Fan, T.Y. and Fine,
D.H., 1978).
-------
K-l
Appendix K
References
-------
K-2
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-------
K-3
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K-4
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Eisenbrand, G. and Spiegelhalder, B. (1977), personal communication.
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Fan, T.Y., Morrison, J., Rounbehler, D.P., Ross, R., Fine, D.H., Miles, W. and
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K-5
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K-6
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