Controversy erupts over hydrogen metallization - C&EN Global

Mar 11, 1991 - Controversy has arisen over experiments indicating that hydrogen becomes a metal at extremely high pressures, with two groups of scient...
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War devastates ecology of Persian Gulf region A fragile desert ecology and an already highly polluted Persian Gulf have been devastated by the war and its aftermath. "This is the largest man-made catastrophe in history . . . and the long-term implications are unclear," says Michael S. Clark, president of Friends of the Earth. Most of the environmental damage was perpetrated by the Iraqis, who deliberately released oil into the Persian Gulf and dynamited or torched Kuwaiti oil wells. But bombing raids and military maneuvers in the desert by U.S.-led coalition forces also contributed. Kuwaiti Oil Co. officials say 85% of Kuwait's oil-producing wells have been destroyed by Iraqi forces or allied bombing, and are ablaze. Michael Renner, a researcher with the Worldwatch Institute, estimates that 2.5 million to 3 million barrels a day of oil is burning out of control. Smoke from these fires is spewing sulfur and nitrogen oxides, heavy metals, and polycyclic aromatic hydrocarbons into the lower atmosphere. The smoke is so thick that it is blocking out sunlight and washing out as a dense, oily soot. Scientists fear increased respiratory problems among children, the elderly, and sick from toxic and carcinogen-ladened soot. Greenpeace spokesmen warn that local water supplies could be polluted and agricultural yields lowered. Smothering the more than 800 wellhead fires and repairing the refineries and tank farms may take two years or more. In the meantime the soot is riding the lower winds for hundreds of miles—north to Turkey, south to Qatar, and east to Iran and beyond. Richard D. Small, a thermal science specialist with Pacific-Sierra Research in Los Angeles, says too little smoke is being created, and it is not being injected high enough into the atmosphere, to induce continental or hemispheric climate changes. Small published his findings in last week's Nature. "It will represent a severe regional environmental pollution event. But the Asian monsoons will not fail. There will be no great tempera-

ture changes. No crop failures are expected," Small says. However, atmospheric scientist Richard P. Turco of the University of California, Los Angeles, believes the "soot will get into the upper level winds (upper troposphere) and cause considerable mischief around the planet." He expects this to happen in the hotter spring and summer months. Monsoon experts tell him that "that there are big enough effects already to dampen the monsoons and turn them off." Before the Iraqis torched the wellheads, they deliberately released stored Kuwaiti crude oil into the gulf in January from two separate sources. These spills plus another large one have combined to leave an oil slick of more than 3 million bbl in the gulf, the Saudi Arabian Meteorology & Environmental Protection Administration estimates. This exceeds by 10 times the Exxon Valdez release in 1989 and rivals the Ixtoc spill in the Gulf of Mexico in 1979, the largest oil spill in history. Tens of thousands of birds are dying, other marine life has been badly affected, coral reefs have been destroyed, and the Saudi shrimp and fishing industry has been wiped out for years. Also at risk are the desalination plants at Jubail and farther south. Lois Ember

Controversy erupts over hydrogen metallization Controversy has arisen over experiments indicating that hydrogen becomes a metal at extremely high pressures, with two groups of scientists questioning the validity of the data. Metallization of hydrogen was first predicted theoretically in 1935, but its demonstration has been elusive. A number of exotic properties are predicted for metallic hydrogen, including very high temperature superconductivity. In 1989, Ho-Kwang Mao and Russell J. Hemley of the Carnegie Institution's Geophysical Laboratory in Washington, D.C., compressed hydrogen at record pressures in a diamond-anvil cell—transforming it,

Hemley: rebuts both groups they said, into an insulating solid, then a semiconductor, and finally a metal-like solid. In 1990, they reported a rise in the reflectivity of compressed hydrogen, also indicating metallization, and they fit these data to a simple theoretical model. However, papers questioning this evidence for hydrogen metallization have recently been published in Physical Review Letters. Physicist Isaac F. Silvera and coworkers at Harvard University repeated some of Mao and Hemley's experiments under more extreme conditions, and found no indication of metallization. "We were able to reanalyze [their] data," says Silvera, "and show that it was inconsistent [and] that you could not interpret metallization based on the model they were using." Silvera believes that hydrogen "may well be metallic in this pressure range, but there's no direct evidence." In a second paper, materials scientists Arthur L. Ruoff and Craig A. Vanderborgh of Cornell University theorize that Mao and Hemley may have observed contaminating aluminum instead of metallized hydrogen. The aluminum, they say, could have been formed by a chemical reaction of ruby powder present in the sample chamber. Hemley rebuts both groups of critics. "Silvera claims there's an inconsistency, [but] if you compare March 11, 1991 C&EN

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News of the Week our spectra with their measurements, they're identical," he tells C&EN. "More important is the fact that their spectra were measured over a very limited energy range so they were unable to see the same features we found." Ruoff and Vanderborgh's theory is incorrect, he adds, because "when one has very low amounts of ruby one sees the same onset of reflectivity." Hemley says a paper of his to be published in April could help clarify the issue. Ruoff, who has seen this paper, says, "It makes it look as if they're backtracking and heading toward agreement with our results," but Hemley calls this "patently false." Research on H 2 metallization continues, with the latest results to be presented at the American Physical Society meeting in Cincinnati later this month. Stu Borman

Anti-clot drug study may hurt biotech sales Results of a massive study of blood clot-dissolving drugs, issued last week at an American College of Cardiology meeting in Atlanta, could have a major impact on sales of highly competitive thrombolytic agents. ISIS-3 (3rd International Study of Infarct Survival) surveyed 46,000 heart attack patients in 16 countries, directly comparing three versions of the agents. The agents were streptokinase from Behringwerke, Eminase (a streptokinase/plasminogen activator complex) produced by SmithKline Beecham, and duteplase [a genetically engineered version of tissue plasminogen activator (TPA)] produced by Wellcome. SmithKline Beecham and Wellcome funded the 18-month study, which was designed by a group at Oxford University. No difference in mortality was found among the drugs. But a key finding was a slight increase in the risk of stroke with Eminase or duteplase. This increased risk, attributed to "probable cerebral bleeding," was about 0.4% higher than for streptokinase. Similar results were found in an Italian study last year, in which the bioengineered drug— in that case, Genentech's recombi6

March 11, 1991 C&EN

nant TPA—faced the decades-older streptokinase. The ISIS-3 results, coupled with growing pressure to trim soaring medical costs, are likely to cause a second look at use of the drugs. Streptokinase costs about $200 per treatment; Eminase about $1700; and TPA, as sold by Genentech, about $2200. Genentech is the only firm to hold U.S. marketing approval for TPA so far, and it dominates the thrombolytic market with $210 million in sales, about a two-thirds

share. However, rising competition from the other two products and results of the Italian study are slowing its sales growth. Genentech stresses that its TPA differs from Wellcome's duteplase used in ISIS-3, which, it notes, is an experimental TPA variant not yet approved for sale. Genentech has gone so far as to sue SmithKline Beecham for implying in advertising that ISIS-3 compares Eminase to Genentech's TPA (C&EN, March 4, page 7). Ann Thayer

Objections to proposed plant safety rules aired Late last week, the Occupational Safety & Health Administration wrapped up eight days of public hearings in Houston on its proposed safety standard for the petrochemical industry. Most witnesses backed the concept of the standard, but many raised objections concerning its implementation. The regulation, proposed last July, aims to provide a systematic approach to accident prevention at facilities that handle flammable, explosive, or highly toxic chemicals. More than 50 companies, industry associations, unions, and public interest groups testified on many of the same issues that surfaced during OSHA's Washington, D.C., hearings on the standard last November (C&EN, Dec. 17, 1990, page 12). The latest hearings made it easier to collect testimony from people in the Houston area—the site of both the October 1989 Phillips 66 plant blast and the July 1990 Arco Chemical explosion, which together killed 40 workers. The hearings were prompted in part by those accidents. At the heart of the standard is the requirement that employers conduct process hazard analyses (PHAs) in their plants. These may enable an employer to "determine where problems may occur, take corrective actions that would be necessary if there were, for example, a failure of safety controls or a failure of redundant systems," says OSHA. Many participants expressed concern over the implementation time frame and costs for performing PHAs. "Implementing and maintaining an effective process safety

management program requires a major commitment of limited resources, both capital and human," said Ramon Lopez, manufacturing and technical vice president for Shell Oil. Texaco Chemical's coordinator of health and safety, Irene L. Jones, testified that the firm "supports the American Petroleum Institute in requesting seven years to complete the initial PHAs." And the Texas Chemical Council pointed out that the cost of such compliance would extend beyond that of the initial PHA to include documentation and training costs, which might involve plant downtime. The hearing also became a forum for debate over the use of subcontractors by petrochemical companies, and how to ensure that they work safely on site. The Oil, Chemical & Atomic Workers International Union reiterated its worry that increasing use of contract labor makes refineries and petrochemical plants more dangerous places to work, and it recommended that the host company take responsibility for training contract workers. Participants commented on many other aspects of the proposed standard, such as its requirements that employers maintain safe operating procedures; maintain mechanical integrity of equipment; manage changes to the processes; conduct incident investigations; develop emergency action plans; and conduct compliance safety audits. OSHA says it expects to publish the final regulation before the end of the year. Susan Ainsworth