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OAR Box 1194 

Prepped by Candice Davis 

Document Number: 

54) ll-F-4 

Docket Number: 

A-90-15 

Printed 5/13/2008 10:52:15 AM Sheet 54 of 89 
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- KWJ . 5 UNITED STATES ENVIRONMENTAL PROTECTION AGENCY 

I AAl/ Z ? WASHINGTON, D.C. 20460 , 

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4-qo-i s 

JUL I 8 1990 OFFICE OF 

AIR ANO RADIATION 

MEMORANDUM 

SUBJECT: Report to Director - The Effects of a Copper-Based Fuel 

FROM: Marilyn yj. McCall, Environmental Protection Specialist 

Fuels Section 

THRU: James W. Caldwell, Chief ..,--:: ^' 1 v ! 

Fuels Section ^''k x % -\'-V! 

'X: V? V-V-"- •'>'•. 

Barry Nussbaum, Chief * - ^ w, . 

Field Operations and Compliance Policy Branch ' .?•'*' n-dXX 

v

".; r.C\ -

L 

TO: Mary T. Smith, Director 

Field Operations and Support Division 

-"•' ('- Vl r. 

Use of Copper-Based Fuel Additives 

Fuel additives containing organometallic compounds can be 

effective when used in diesel-fueled engines in two modes: 1) in 

the combustion chamber during the combustion cycle, and, 2) in the 

exhaust system after the combustion chamber. It is important not 

to confuse the two conceptual uses of organometallic additives in 

diesel-fueled engines. 

Organo compounds of barium, calcium, manganese and iron (and 

others) have proven effective in the combustion chamber during 

combustion in suppressing smoke or soot particulates. These 

compounds affect engine-out exhaust particulates.(1)* I have 

reported on the effects of these types of diesel fuel additives 

previously submitted to you on the subject of barium-based diesel 

fuel additives.** 

* Numbers in parentheses designate references at the end of the 

memo. 

** McCall, Marilyn, Air Toxics Report to Director - Barium-Based 

Fuel Additives, June 26, 1990. 
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Additionally, use of a copper-containing additive in a 

combination with a particulate trap to reduce particulates has 

proven effective in the exhaust system after the combustion 

chamber.(1) When various metals such as copper, manganese, and 

lead are deposited along with the soot in the trap, the 

autoignition temperature of the mixture is lowered to a level where 

exhaust temperatures can ignite and allow complete oxidation of the 

soot to occur. This regenerates the filter to control back 

pressure buildup in the trap„(1) 

Even though metallic additives produce particulates via their 

products of combustion„ they are applied to fuels to give a net 

positive resulto Consideration should be given to their potential 

long-term engine durability and health effects.(1) 

My research shows that there is no industry-accepted standard 

test method to evaluate fuel and fuel additive effects on 

particulates. Many investigators, however, are testing per 

procedures and guidelines set forth by the EPA. EPA is currently 

developing first-time testing requirements for fuels and 

additives.(1) As an aside on this subject, in my research, I ran 

across an interesting document published by the National Research 

Council's Transportation Research Board which gives guidelines to 

transit operators for evaluating fuel additives. This body 

recommends, among other procedures, that additives undergo several 

laboratory tests of fuel properties in the evaluation process. The 

test procedures are mainly those set down by ASTM procedures for 

testing various fuel properties such as pour point, cold filter 

plugging temperature„ accelerated stability, gravity, particulate 

contamination, etc The accelerated stability test measures the 

tendency of the fuel to form insoluble deposits resulting from 

exposure to oxygen or heato The particulate contamination test is 

a sensitive indicator of particles that could plug fuel filters or 

cause increased injector and piston ring wear. It was designed for 

aviation fuels but can be useful for diesel fuels.(2) This aside 

is included here because I believe that some mention of evaluation 

of fuel additives must be made as an important aspect of the 

investigation of the potential effects of any fuel additive. 

Lubrizol Company has developed a new copper-based diesel fuel 

additive for use in a trap-based diesel particulate control system 

which heavy duty engine and light-duty vehicle manufacturers might 

wish to use to meet future, more stringent, particulate standards. 

This additive mechanism is being looked at by the EPA as a 

potentially viable means for some engines to meet the stringent EPA 

standards set to begin in 1994. 

Lubrizol has submitted their research on this copper additive 

system in a report entitled "An Analysis of Possible Health Effects 

Due to the Use of a Copper Diesel Fuel Additive," dated May 1990. 
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Their technical findings of this system are presented in a paper 

entitled "An Experimental Evaluation to Determine the Effect of an 

Organometallic Fuel Additive on Particulate Trap Regeneration," by 

their Messrs. Levin and Koehler, (undated). Lubrizol gave a 

presentation on the effects of this system to EPA on May 7, 1990, 

at Ann Arbor, Michigan. 

The control strategy that Lubrizol has developed relies on a 

trap system which filters particulate from the exhaust gas, 

accumulating particulate until regeneration is initiated. During 

accumulation, the mass of particulate increases, resulting in a 

proportional increase in back pressure. Regeneration must be 

initiated when a maximum back pressure is reached or when continued 

particulate accumulation would be expected to result in a 

regeneration with temperature excursions known to cause excessive 

thermal stress within the filtration media. Regeneration is 

typically initiated by operating the engine at relatively high 

speed/load modes, adding energy to the trap via an external source, 

or by adding a catalyst to reduce particulate activation energy. 

Copper acts as the catalyst because of its superior effect in 

reducing the activation energy of particulate combustion.(3) My 

research shows that in other studies involving use of additives 

containing copper plus nickel, and additives containing copper plus 

cerium that over 95% of the fuel additive was collected in the 

trap, releasing about 5% of the compound into the atmosphere.(1) 

Lubrizol believes that this is hardly a drop in the copperemissions bucket. 

I have read Lubrizol's report on the possible health effects 

of using a copper diesel fuel additive. Their report strikes me 

as being very thorough. Their bibliography reveals that we 

(Lubrizol and I) consulted in common, several literature sources 

on health effects of emissions of copper. A discussion of my 

findings follows. 

Copper and its Effects in the Environment 

The concentration of trace metals in the atmosphere have 

become a matter of considerable concern for many reasons. Metals 

in air (a) may be a health hazard to human beings and animals; (b) 

can act as a catalyst in atmospheric reactions? (c) may promote the 

corrosion of materials; (d) may initiate far-reaching changes in 

the receiving ecosystems; and (e) in association with suspended 

particulate matter may induce changes in the climate.(4) I will 

try to limit my discussion to (a) only; for to discuss all four 

concerns would require a very lengthy treatise on the subject. 

Three principal human sources of pollutant copper in the 

atmosphere are copper production and handling (46% of total 

anthropogenic emissions), iron and steel production (10%), and 
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fossil fuel combustion (11%).(4) 

Several studies have addressed disposition of copper in flyash samples from fossil fuel combustion sources. The mechanism by 

which the fine copper-rich aerosols are formed include (a) 

condensation of the volatilized copper or its compounds, (b) 

preferential uptake of copper by some solid or molten particles, 

and (c) chemical reactions with the condensable gases, especially 

S02 and the nitrogen oxides. In the presence of oxygen, 

particulate copper oxides may catalyze the oxidation of S02 and in 

the process become converted to copper sulfate. The results 

obtained show that the copper is mostly concentrated in the 

smallest (respirable) particles. Very little is currently known 

about the chemical composition of copper aerosol, however, several 

studies show that a large fraction of the copper in atmospheric 

aerosols occurs in the particle sizes that are the most hazardous 

to human beings and other organisms, i.e., the smaller-diameter 

size.(4) 

The influence of particle size on the disposition and 

retention of particulates in the respiratory system has been 

investigated (Morrow, 1964; Stuart, 1976; Yeh et al., 1976). For 

cupreous (copper-containing) particles of about 1.0-/im mass median 

diameter (MMD), approximately 50 to 60% of the inhaled copper is 

deposited in the pulmonary compartment, 20 to 30% in the 

nasopharyngeal compartment, and <10% in the tracheobronchial 

compartment. A high proportion (50 to 80%) of the <l-/nm particles 

retained in the respiratory system is absorbed in the 

bloodstream.(4) Lubrizol's analyses cited some studies that were 

done later than those mentioned above which showed slight variances 

of particulate sizes and disposition efficiencies. 

No studies have specifically addressed atmospheric residence 

times for cupreous aerosols. By analogy with work done on general 

particulate residence times, it is surmised that the residence time 

for cupreous aerosols in unpolluted troposphere is 2 to 10 days. 

In urban and polluted areas the residence time may be more than 4 

days for particles of small diameters.(4) 

Health Aspects of Copper 

Under ordinary circumstances copper is a benign agent, but 

when human beings and other animals are exposed to excessive 

concentrations of the metal in any of its forms there may be mild 

to serious or even life-threatening consequences. Copper is 

essential to human life but is also potentially lethally toxic. 

Two distinct and specific genetic regulatory mechanisms exist in 

normal human beings. One appears to facilitate the transmembranous 

transfer of copper. Absence of this mechanism results in a 

hereditary form of copper deficiency which is fatal despite 
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attempts at either oral or parenteral treatment with copper. A 

second mechanism, transmitted as an autosomal recessive, seems to 

be essential to the excretion of ceruloplasmin copper from hepatic 

lysosomers into bile, and may be responsible for the maintenance 

of the normal zero balance of copper. In patients in whom this 

second type of genetically transmitted mechanism is absent, 

Wilson's disease or human chronic copper toxicosis, ultimately 

develops and is fatal if untreated.(5) 

Toxicosis due to copper is avoided in genetically normal 

individuals both by the action of this second mechanism and also 

by virtue of the fact that the essentiality of copper acts only 

through specific copper proteins. Such a metal protein complex 

reduces the concentration of free copper ions throughout the body 

and thus avoids the toxicity that is as inherent in copper ions as 

it is in ions of such nonessential metals as lead and mercury.(5) 

Acquired deficiency of copper can be effectively treated by 

administration of the element. Acquired or inherited toxicosis of 

this metal can be treated by use of a chelating agent, which 

promotes the excretion of copper.(5) 

EPA proposed a criteria document for copper in drinking water 

for the EPA Office of Drinking Water in February 1987. Copper has 

been identified by that Office as a pollutant in drinking water and 

they are presently setting maximum contaminant level goals (MCLG) 

for copper (and lead). These standards will be promulgated in 

December 1990. A phone call to that Office revealed that the MCLG 

for copper will be 1.3 mg/L. 

Copper compounds can be absorbed by all three environmental 

routes: dermal, oral and inhalation. Normal daily intakes of 

copper are 2.5 mg/day, mostly from food and water, with a slight 

contribution from air. The total body content of normal adult 

humans is ~ 70-120 mg of copper, most of which is located in the 

liver.(6) 

EPA found that there was limited information on the presence 

of copper in ambient air. Information was available from a 

nationwide study on copper concentrations in ambient air for the 

years 1977-1983 (U.S. EPA 1984). Concentration samples analyzed 

ranged from 0.003 - 7.32 p,q/m3, with a range of median values for 

different cities and years of 0.004 - 1.79 /ig/m3 and mean values 

of 0.0043 - 1.96 /Ag/m . (6) Using the high value of the range of 

median levels and assuming a ventilation rate of 20 m3/day for the 

average adult male, the intake of copper from air would be 

35.8 /ag/day. (6) 

Acquired chronic toxicosis in humans is more unusual than the 

acute form.(5) The literature is replete with studies regarding 

the nutritional essentiality of copper, but copper toxicity from 
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chronic exposure has not been well investigated.(6) 

Under ordinary circumstances, it seems almost impossible to 

overwhelm the body°s defense against copper toxicosis by oral 

ingestion of the element° Chilean copper miners eat their lunch 

for as long as 20 years, in an atmosphere cloudy with 2% copper ore 

dust. Analyses of the copper contents of liver and blood in a 

small number of these miners have been normal.(5) 

Vineyard workers wlho spray grapes with copper arsenate have 

shown some toxic effects, but these are not clearly related to 

copper.(5) Villar (1974) reported observing copper-containing 

granulomas in the lung, liver and kidney of a deceased patient who 

had been occupationally exposed to Bordeaux mixture (an aqueous 

solution of lime and 1-2% copper sulfate) during the spraying of 

vineyards. Pimental and Menzes (1975) reported finding coppercontaining liver granulomas in three patients with a history of 

using Bordeaux mixture involved in vineyard spraying.(6) I found 

many references to various studies of vineyard workers being 

exposed occupationally to this "Bordeaux" mixture. Lubrizol's 

report refers to studies by several investigators (Pimental and 

Marques, 1969; Villar, 1974; Pimental and Menzes, 1975; Plamenac 

et al. 1985) and their reports of a syndrome known as "vineyard 

sprayer's lung," which may involve symptoms such as lesions in the 

lungs, dyspnea, decreased appetite, weight loss, and general 

weakness. Lubrizol dismisses these studies as not conclusive 

because none of the reports gave estimates of the levels of 

exposure. Also they state that vineyard workers may also be 

exposed to other agents such as arsenic compounds in addition to 

Bordeaux mixture and it is not clear in the studies that copper 

compounds were the sole cafstafel agents in the incidences of the 

illness.(3) 

Gleason (1968) reported symptoms of metal fume fever (general 

discomfort, fever, sensations of chills or warmth and stuffiness 

of the head) in three workers exposed to fine copper dust at 

concentrations of ®o®3 - ©„12 mg/m3. (6) (The Federal standard for 

copper fume is 0,1 mg/ur1; for copper dusts and mists, it is 

1 mg/m3. (9)) Metal fume fever symptoms were absent in these workers 

after the installation of local exhaust ventilation, which reduced 

the airborne copper concentration to <0.008 mg/m3. (6) 

The potential for acute poisoning from ingestion of copper 

compounds has long been recognized. The unwitting ingestion of 

many types of food and nonfood items containing copper has produced 

symptoms of copper poisoning ranging from Gl disturbances, 

headache, dizziness, metallic taste, to death. In general 

instances, the exposure is to copper sulfate leading to the theory 

that some of the toxicity may be due to the sulfate compound. 

Studies of cases of copper poisoning in children indicate that 

children may be more susceptible to copper toxicosis.(6) 
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Other effects of copper sulfate acute poisoning include 

hemolytic anemia, Glucose-6-Phosphate Dehydrogenase (G-6-PD) 

deficiency, renal failure, hematuria and death (Walsh et al., 1977; 

Roberts, 1956; Chugh et al., 1975). These effects were reported 

to occur at doses between 3 and 600 g of copper sulfate (0.76 -

152.4 g CU).(6) It has been suggested that persons with Wilson's 

disease, deficiencies in G-6-PD activity, and those having 

occupational exposure to copper may be at risk from the toxic 

effects of copper (U. S. EPA, 1980).(6) 

EPA concludes that inadequate data preclude calculation of a 

Reference Dose as there are no data indicating that human exposure 

to copper results in chronic toxic effects to normal individuals. 

Based on the available data, EPA cannot classify copper as a human 

carcinogen or mutagen.(6) 

Conclusions 

Consideration should be given by EPA on the use of metallicbased fuel additives as they are used in diesel-engined vehicles 

and the potential long-term effects of these additives on health 

and engine durability. The aim of this paper is to present my 

findings on the potential impact of the use of a copper-based fuel 

additive. My findings indicate that there are a lot of unknowns 

of the long-term effects of such a fuel additive. This office's 

role, as I see it, should continue to be one of monitor of such 

use, especially if there is an increase in the use of metallicbased fuel additives. 
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References 

1. Tupa, R. C., C. J. Doren, The Lubrizol Corp., "Gasoline and 

Diesel Fuel Additives for Performance/Distribution Quality -

II," SAE Paper 861179, 1986. 

2. National Research Council, Transportation Research Board, 

Washington, D. C., "Diesel Fuel Quality and Effects of Fuel 

Additives," 1984. 

3. Levin, Dr. M. D. and D. E. Koehler, "Lubrizol Diesel 

Particulate Filter Development - An Update" EPA - Lubrizol 

Meeting Agenda, Ann Arbor, MI, May 7, 1990. 

4. Nriagu, Jerome 0., Ed., Copper in the Environment. Vol. I, 

Canada Center for Inland Waters, John Wiley and Sons, Inc., 

New York, 1979. 

5. Nriagu, Jerome 0., Ed., Human Health Effects of Copper. Vol. 

II, Canada Center for Inland Waters, John Wiley and Sons, 

Inc., New York, 1979. 

6. U. S. EPA Environmental Criteria and Assessment Office, 

"Drinking Water Criteria Document for Copper," Cincinnati, OH, 

February 1987. 

7. Roth Associates, Rockville, MD, Prepared for Lubrizol Business 

Development Company, "An Analysis of Possible Health Effects 

Due to the Use of a Copper Diesel Fuel Additive," May 1990. 

8. McCall, Marilyn, "Air Toxics Report to Director - Barium-Based 

Fuel Additives," June 26, 1990. 

9. Sitting, Marshall, Hazardous and Toxic Effects of Industrial 

Chemicals. Noyes Data Corporation, Park Ridge, NJ, 1979. 

10. RAO, V. D., et al., "Advanced Techniques for Thermal and 

Catalytic Diesel Particulate Trap Regeneration," SAE Paper 

850014, 1985.