Review of the document "Toxicological and Performance Aspects of Oxygenated Motor Vehicle Fuels" produced by the National Academy of Sciences Washington, DC Released June 19, 1996 Due to widespread public complaints of health problems attributed to the use of the chemical methyl tertiary butyl ether (MTBE) in gasoline, several government agencies, including the Environmental Protection Agency, the National Institutes of Environmental Health Sciences, the National Oceanic and Atmospheric Administration, and the Center for Disease Control and Prevention, organized a set of expert committees to review the status of this highly controversial field. The health effects were studied by two separate committees, one based in the White House Office of Science and Technology Policy (OSTP), and the other organized through the Health Effects Institute (HEI) of Cambridge, MA. None of these groups did any actual research into the public health effects of MTBE in gasoline, they only reviewed existing information. Essentially, the National Academy of Sciences (NAS) report is a study of studies of studies on MTBE. Here I offer a study of the study of the studies of the studies on MTBE. (!) The conclusions of the NAS review can be summarized as follows: (I) it is becoming clear that using MTBE or other oxygenate chemicals in gasoline does not lead to a significant reduction in winter carbon monoxide (CO) levels, (II) water pollution by MTBE is a possibly significant problem that has not been studied, (III) existing data does not rule out the possibility that some individuals are suffering from illness produced by MTBE. One common failure of both the NAS report and the two reports it summarizes is selective reading of anecdotal evidence that MTBE is harming people. For example, they mention public complaints in Alaska, Montana, New Jersey, and Wisconsin, but fail to mention or consider similar complaints that have come from Maine, Connecticut, Pennsylvania, Texas, and Colorado. The OSTP received a large number of letters from individuals in those states complaining of bad health effects from MTBE. The NAS report also failed to mention the huge problem with water pollution from MTBE that has been extensively documented by the North Carolina State Department of Health. In quoting from the NAS review, I have occasionally added emphasis. I: Regarding the effectiveness of oxygenates to reduce CO. The NAS report makes it crystal clear, in page after page of succinct analytical prose, that the actual benefits from oxygenating gasoline in terms of reducing CO and other air pollutants are negligible. Here are a few of the more interesting quotes: page 3: "... winter ambient CO reductions attributable to oxygenated fuels have been as low as zero and as high as about 10%." page 4: "Much of the available data suggests that increased NOx emissions have resulted from the use of oxygenated fuels. Any increase in NOx emissions could be detrimental in ozone nonattainment areas where exceedences have occurred during the period of the oxygenated-fuels program". Comment: Data collected from public air quality reports by the anti-MTBE group "Oxybusters" in New Jersey indicate that in the Philadelphia area ozone levels during the summer of 1995, the first with reformulated gasoline, were not reduced. My analysis of this data, spanning 1993, 94, and 95, indicate that elevated summer temperatures in 1995 can not explain the increase in ozone at that time. Furthermore, two studies of exhaust emission published in the peer reviewed scientific literature (1,2) indicate that the reformulated gasoline did not significantly reduce those reactive hydrocarbons that are thought to contribute to ozone. This result, combined with the observation of the NAS committee, suggests that RFG may even increase ozone levels. page 31: "... it is difficult to generalize about the effect of using oxygenated fuels on CO emissions. However, during closed-loop operation with perfect control there should be little change in CO emissions; the control sensor should maintain the same stoichiometry and therefore the same CO emissions, irrespective of fuel" This is a bit technical and needs explanation. The amount of CO and other pollutants created in car exhaust depend in a subtle way on the exact ratio of fuel to air going into the engine. Modern cars use a sophisticated computer-controlled feedback loop which senses oxygen in the exhaust and tries to maintain the optimum fuel/air ratio. This is what is called "closed loop" operation. It is widely acknowledged that this technology has been a major contributor to the reduction of CO emissions from cars in recent years. However, as the NAS report emphasizes, even this system will not operate correctly when the car is cold. They suggest this is the reason why no improvement in winter time CO pollution has been observed from using oxygenated fuels. page 32: "While the annual variation in CO levels has decreased, the trend of average CO level shows no change since winter oxygenated fuels were introduced." page 35: "... some of the data indicate tendencies for increased CO emissions with oxygenated fuels" page 39: " The data from the interagency report show that oxygenated fuels do increase NOx emissions ..." page 40: " ... in some cases CO concentrations have actually increased." page 42: "Review of the existing data reveal a lack of measurements at conditions relevant for winter conditions..." page 50: "The enleanment effect of oxygenated fuels presents the potential for increased NOx emissions from motor vehicles. Furthermore, much of the available data suggests that such an increase does occur. Any increase in NOx emissions could be detrimental in ozone non-attainment areas where exceedances have occurred during the period of oxygenated fuels program." (II) Regarding the effect of MTBE polluting drinking water. The NAS report has one short chapter which mostly emphasizes what is not known. They ignore the major problem with MTBE water pollution in North Carolina, which has withdrawn from the oxygenated fuel program for that reason. It is generally acknowledged that MTBE, because of its relatively high water solubility, is much more of a potential problem than are other gasoline components which are much less water soluble. Furthermore, the report emphasizes that whereas conventional gasoline components are eventually degraded by natural biological processes in the soil, MTBE is not. page 65: "More needs to be known about the biodegradation of MTBE ... in surface water, soil, and ground water". Comment: I suspect that if MTBE is "degraded" biologically an end product may be the highly toxic chemical TBF. It is known(3) that one proposed method to "degrade" MTBE, namely exposing it to ozone, creates mainly TBF. Since the publication of the NAS report, news reports indicate that the city of Santa Monica, California, has found huge concentrations of MTBE in three of its five municipal water wells. This has required shutting down the affected wells. (III) Regarding negative effects on human health from MTBE gasoline. The NAS report was surprisingly critical of both the HEI and OSTP reports, saying that existing studies do not rule out any such effects, and in fact much information now available does suggest that many of the reported effects may be real. page 82: "... in both Anchorage and Fairbanks there was an increase in visits for headaches in the winter of 1992-93, when compared with the winter of 1990-91... The HEI report does not comment on this finding at all..." pages 82-83: "These results are internally consistent and suggest that workers occupationally exposed to MTBE are at greater risk for the development of acute health effects." page 87: "... respondents in Chicago still reported a higher prevalence of eye irritation, headache, and sinus problems while pumping gas." This requires some explanation of background. In early 1995, just after MTBE reformulated gasoline (RFG) was introduced into Milwaukee, literally thousands of people complained it was making them sick. This resulted in much publicity which induced the Wisconsin Department of Health to do a telephone survey. The survey results indicated that 23% of the people in Milwaukee felt they had unusually severe health problems. However, in Chicago, where RFG was also used, the number was only 6%, the same as in rural Wisconsin, which did not have RFG. This lead to the conclusion that people in Milwaukee were imagining that MTBE was making them ill. Thus, the observation that people in Chicago were reporting increased problems with eye irritation and sinus problems is highly significant. Incidently, my own recent research, working with the Philadelphia Department of Health, indicates enormous increases in eye irritation and sinusitis since MTBE oxygenated gasoline was introduced in 1993. page 89: "The OSTP report concludes ... that oil, chemical, and atomic workers have reported many of the same symptoms that were reported by motorists in Alaska and other symptoms as well, including sinus problems, fatigue, and shortness of breath." page 90: "Both the HEI and OSTP reports fail to acknowledge that while largely anecdotal, these occupational studies are consistent with the studies of Alaska, Connecticut, and New Jersey, all of which reported that workers exposed to higher levels of MTBE may experience symptoms due to those exposures." pages 94-95: "... data from many of the occupational studies of exposed workers. As stated previously, these studies indicate that workers exposed to greater concentrations of MTBE experience more symptoms." page 97: "epidemiologic data ...do indicate that some people have experienced acute symptoms associated with exposure to gasoline containing MTBE." page 99: " some data ... suggested a higher prevalence of MTBE-associated symptoms among those with physician- diagnosed allergies." (IV) What about cost/benefit analysis? In other words, are there any benefits to oxygenating gasoline? The sole proposed benefit to reducing CO levels (assuming they are reduced!) is to reduce angina pain in people with heart disease. The attitude of the NAS committee is that no data exist to support that idea. pages 119-120: "Although the goal of the winter oxygenated-fuels program is to reduce ambient CO levels to protect public health, particularly among patients with cardiovascular disease, data are not available to evaluate the effectiveness of the program..." What baffles me is how anyone with medical knowledge could even suggest that the small reduction in CO would actually help anyone with cardiovascular disease. Exposure to high levels of CO will, over a period of several hours, lead to a reduction in the ability of our red blood cells to carry oxygen. However, the known facts of this effect indicate that this is unlikely to be a significant factor today. The current EPA limit for acceptable CO concentration is 9 parts per million (ppm). At this level, after 8 hours of exposure it is known that a human will lose about 2% of his blood's oxygen carrying capacity. This effect is due to saturation of hemoglobin by CO. So, if we assume that oxygenated gasoline lowers CO by 10% (a generous assumption!) this would imply an improvement of only 0.2% in the blood. No physician or physiologist that I have spoken with has suggested that this small improvement is of any consequence at all, even for people with serious cardiovascular disease. Thus it seems clear that the whole premise that oxygenating gasoline will improve the health of anyone is patently absurd! I presented this argument in my critique of the HEI report, which was apparently ignored by the NAS committee. (V) What about TBF? TBF stands for tertiary butyl formate. It has been shown in three laboratory experiments to be the main byproduct of the degeneration of MTBE under certain conditions in the atmosphere. It has also been shown to be the main product of the use of ozone to treat water contaminated with MTBE. I was the first to call attention to the possibility that TBF in the air may be a significant public health problem(4). There is no information in the published scientific literature on the toxicity of TBF. However, an industrial safety sheet indicates it is extremely toxic, that "inhalation can be fatal", and that anyone working with this substance should use a "self contained respirator". page 74: "Routine monitoring of ... tertiary-butyl formate should be initiated in communities where MTBE is used. (TBF has the potential to accumulate and persist in the atmosphere and its toxicity is unknown.)" page 80: "TBF is one of the major photooxidation byproducts of MTBE. If TBF levels are increased in the ambient air due to MTBE use, the available literature on TBF toxicity needs to be reviewed in the report... Additional studies to characterize the acute and chronic toxicity of TBF may need to be added." (VI) My reaction. I have maintained for several years that the use of MTBE in gasoline is causing widespread public health problems. I base this partly on my own pattern of symptoms, which are both respiratory and neurological, and which disappear when I travel to regions where MTBE oxygenated gasoline is not used. I have acquired a huge amount of "anecdotal" data in support of this conviction, including case histories of literally hundreds of other people. I have written over 400 letters and faxes to various scientists, physicians, and officials, most of which have been ignored. I have published one letter in the prestigious scientific journal Archives of Environmental Health. I sent voluminous documentation of my experiences and observations to the HEI committee; this was totally ignored. I then wrote a detailed critique of the HEI report which was submitted to the NAS committee; this apparently was also ignored. My main contention is that the health effects from MTBE are not limited to direct exposure to gasoline, but are being felt throughout the community from pollution of the ambient air. I suspect that the main toxin is not MTBE itself, but some byproduct chemical. I have suggested that TBF could be causing the problem, but this could be wrong. Another idea I am examining is the production of tertiary butyl nitrite (TBN). However, I do not see why it is necessary to first identify the toxic chemical that is active before looking at the epidemiologic data that support this idea. One of my important ideas is that asthma has been increased by the use of MTBE in motor fuel. This has been going on not only since 1992, when oxygenated gasoline was introduced to many cities, but since 1979 when MTBE was approved as an octane enhancer in gasoline. Despite many attempts, I have failed to convince any public health authorities (with the important exception of the Philadelphia Department of Health) to even examine this possibility. There seems to be a very deep skepticism about this idea; that baffles me. Many asthma experts argue that asthma has been going up "all over the world"; therefore, they argue, MTBE can not be the cause. This is both incorrect and illogical. There is no logical reason why MTBE could not be increasing asthma in some places, while in other places some other factor (such as increased industrialization) is more important. Furthermore, it is not true that MTBE has been used only in the United States; many industrial countries have been using it for 10 to 20 years as an octane enhancer. Interestingly, several supporters of MTBE have argued that the widespread use of MTBE "all over the world" is evidence that it is benign. My problem is to get the asthma specialists and the oil company executives to talk to each other! It is a matter of great frustration for me that the NAS committee failed to even consider this possible association. Some of the symptoms found to be associated with MTBE usage, namely eye irritation, sinusitis, and cough, are typical of exposure to respiratory irritant chemicals. TBF, as an ester of formic acid, is expected a priori to be a potent respiratory irritant. It is widely accepted that chronic exposure to even low levels of irritant chemicals can induce asthma. So how does one explain the apparent reluctance of the various scientists on these various committees to even acknowledge the possibility that MTBE may be causing asthma? I am now collecting epidemiologic data from the Philadelphia region that show a dramatic increase in asthma in this region since MTBE oxygenated fuel was mandated in 1992. The suggestion that this rapid increase is attributable to increased concentrations of sub-micron particulate pollution is contradicted by data from the Philadelphia Department of Health. Perhaps these data will convince someone in power to look at this idea. Meanwhile, I continue to suffer from a drastically reduced quality of life that I attribute to MTBE in gasoline. I never go out at night in the Philadelphia area because my symptoms are extremely sensitive to sunlight, i.e, the offending substance is destroyed by sunlight. I depend on air filtering machines to live in my home. For this reason I try not to go into Philadelphia on cloudy days, and I do not travel overnight to cities where MTBE is mandated in gasoline. I also use an air filtering machine in my car. For my wife's birthday dinner, we drove to Reading, Pennsylvania, where RFG is not used, and enjoyed our evening free from these symptoms. I have demonstrated on several occasions that my symptoms disappear upon travel to regions without mandated MTBE. I live with the cloudy day effect on a daily basis. I enclose a list of various fallacious assumptions usually made by those who argue that MTBE is without negative health effects. I welcome comments from anyone interested in this problem. Peter M. Joseph, Ph.D. Professor of Radiologic Physics in Radiology July 4, 1996 email: joseph@rad.upenn.edu REFERENCES 1. Hoekman SK. Speciated Measurements and Calculated Reactivities of Vehicle Exhaust Emissions from Conventional and Reformulated Gasolines. Environ. Sci. Technology 1992;26:1206-1216. 2. Kirchstetter TW, Singer BC, Harley RA, Kendall GR, Chan W. Impact of Oxygenated Gasoline Use on California Light-Duty Vehicle Emissions. Environ. Sci. Technology 1996;30:661-670. 3. Leitner NKV, Papaihou AL, Croue JP, Peyrot J, Dore M. Oxidation of Methyl tert-Butyl Ether (MTBE) and Ethyl tert-Butyl Ether (ETBE) and Combined Ozone/Hydrogen Peroxide. Ozone Sci. and Eng. 1994;16:41-54. 4. Joseph PM. Letter: Atmospheric Byproducts of MTBE as a Source of Community-wide Illness. Arch. Env. Health 1995;50:395-396. FALLACIOUS ASSUMPTIONS OF EXISTING INTERPRETATIONS OF DATA 1. Only MTBE is causing problems, not TBF or TBA; i.e. symptoms should correlate with blood [MTBE]. 2. No TBF or other toxics are created in automobile exhaust. 3. Ambient TBF levels are too small to create problems. 4. People with MCS are most likely to suffer; or, all chemical sensitization is psychological. 5. Irritation symptoms are a "short term" effect. 6. TBF is no more irritating than ethyl formate. 7. Asthma increase is limited to minority people in cities. 8. Asthma increase is due to sub-micron particles. 9. Respiratory infections are not affected by TBF. 10. Cloudy days and sunshine are irrelevant. This is why existing studies, including the National Research Council, have missed this important public health problem! CHANGES IN NUMBERS OF OFFICE VISITS FOR DISEASES INFLUENCED BY ATMOSPHERIC IRRITANTS IN PHILADELPHIA SINCE 1993. June 27, 1996 Preliminary Report by Peter M. Joseph, Ph.D., University of Pennsylvania with collaboration by Warner Tillack, Phila. Dept. Health. This data base is known to be underreported for January and February of 1993. Therefore, I have defined a year as beginning in March and ending the next February. The increases reported are for yearly totals, comparing 1993-94 to 1995-96, i.e. spanning 36 months. Gasoline oxygenated with at least 11 % MTBE was introduced in November 1992. Except for asthma, all of these data are for adults only because the pediatric diagnosis forms were changed at the end of 1993. The diagnostic category asthma did not change. Part I: Diseases possibly influenced by respiratory irritants Diagnosis 1993 1994 1995 % Increase (93-95) Allergic Rhinitis 1646 1861 2105 27% (increased only in winter months) Winter Rhinitis 311 401 460 48% Asthma 4848 6197 6972 44% (minimum each midsummer, rise each winter) Conjunctivitis 362 434 606 67% Chronic Bronchitis 480 439 515 7% Dyspnea 61 89 122 100% Otitis 754 846 980 40% Chronic Sinusitis 699 949 1191 70% Part II: Control diseases not thought to be influenced by environmental pollutants. All Visits 203,907 230,474 224,732 10% hypertension 32,459 35,107 36,063 11% diabetes 21,343 22,056 20,853 -2.2%