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Hydrogen Diving: The Good, The Bad, the Ugly

In the preceding blog post, I reminded the reader that the Earth’s supply of helium is limited. It is not a renewable resource.

Being a diving professional, I am not concerned about the consequence of a helium shortage on party balloons. But I am thinking about the potential consequences on diving.

So, knowing that hydrogen has both good and bad traits, it would be prudent to begin thinking about whether or not there is a way to safely substitute hydrogen for helium in technical, scientific, commercial and military diving.

Perhaps the word “bad” is too much of an understatement. Perhaps “horrible” would be a better descriptor for something like the Hindenburg disaster.

With that sobering reminder of what can happen, we now cautiously move on to the science.

First, we begin with the explosion hazard of hydrogen in binary mixtures of hydrogen and oxygen.

For diving in the 10 to 20 bar range, 326 to 653 fsw range, the upper explosion limit is 94.2 molar percent. So that means that if a binary gas mixture contains 96% hydrogen and 4% oxygen, it should not explode when ignited.

Those underlined words are important. An explosive mixture of hydrogen and oxygen will not explode without an ignition source. Proof of that is exhibited in many college introductory chemistry lectures, and documented in the following YouTube video.

Arne Zetterström

As a forecast of our potential future, during World War II, Sweden was deprived of a ready source of helium coming from the U.S. and elsewhere. So, the clever and industrious Arne Zetterström conducted a series of experimental deep, hard hat dives from 1943 to 1945 using a mixture of 96% hydrogen and 4% oxygen on dives ranging from 12 to 17 bar.

Once at depth, Zetterström switched from a non-hydrox gas mixture to the “hydrox” gas mixture. His initial test dive was to 111 msw (362 fsw, 12 bar), progressing through six dives to a maximum depth of 160 msw (522 fsw, 17 bar).

That dive series was successful. Unfortunately, on the last dive on 7 August 1945, Zetterström died tragically when his dive tenders mistakenly pulled him directly to the surface from the bottom depth of 522 fsw. He died from fulminant decompression sickness.

From the above table we see that modern measurements confirm that Zetterström chose his gas mixes wisely. At a 96 mol% of hydrogen, he was above the upper explosion limit. If there had been an unexpected ignition event, his breathing gas mixture would not have exploded.

I have confirmed the oxygen partial pressure for Zetterström’s dives using PTC Mathcad Express 3.1 and will share the process.

First, I show pressure conversions familiar to Navy divers and diving scientists, but not known to most others.

For Zetterström’s 111 msw (362 fsw) dive, the partial pressure of oxygen (PO₂) would have been 0.478 atm, at the top end of the target range (0.4 to 0.48) for U.S. Navy chamber oxygen atmosphere during saturation diving. A PO₂of 0.48 is believed to be the highest PO₂ tolerated for extended periods. Saturation dives sometimes last over a month.

For Zetterström’s 6th and last dive, to 160 msw (522 fsw), the oxygen partial pressure was 0.7 ata, about half of what it normally is in modern electronic rebreathers with fixed PO₂.

A far more detailed story of the Zetterström Hydrox dive series can be found in this book.

Arne Zetterström Memorial Dive

In 2012, the Swedish Historical Diving Society and the Royal Institute of Technology (KTH) Diving Club, Stockholm, conducted an Arne Zetterström Memorial dive to a relatively shallow depth of 40 msw or 131 fsw. The original 96% – 4% ratio of hydrogen and oxygen was maintained, resulting in a gas mixture with a PO2 of 0.20 atm.

As reported in the KTH Dive Club’s Dykloggen (dive log) report of July 2012, the team lead was Ola Lindh, Project Leader and Diver. Åke Larsson, another diver, contributed the following information about that dive.

The Hydrox divers used open circuit scuba, with back mounted air, and for decompression, bottles of hydrox and oxygen.

The Swedish divers did not go deeper than 131 feet because they were just above the mud at that depth in a quarry. Plus, they did not yet have details of Zetterström’s decompression plan for deeper diving.

Today, they do possess the wartime hydrogen decompression plan, so deeper hydrogen dives may be forthcoming.

Three gas mixtures – hydrogen, and air (nitrogen and oxygen)

When you mix an inert gas like nitrogen (or perhaps helium?) with hydrogen and oxygen mixtures, that greatly reduces the explosion hazard. But as this video shows, sooner or later the ratios might change enough to become explosive.

Naval Medical Research Institute

I spent 12 years working as a diving biomedical researcher at the Naval Medical Research Institute (NMRI) in Bethesda, MD.

Main entrance to the Albert R. Behnke Diving Medicine Research Center, at NMRI.

My laboratory was in the Behnke Diving Medicine Research Center building, but the hyperbaric hydrogen facility was situated a safe distance behind the main building. In the unlikely event of an explosion, the main Behnke facility and its hyperbaric chamber complex would be preserved.

The hyperbaric hydrogen facility was used to test the effects of high-pressure hydrogen and biochemical decompression on pigs, rather than risk human divers. And all of that was done safely, thanks to the professionalism of Navy divers and scientists.

Dr. Susan Kayar checking on the hydrogen diving pigs.

Kayar, a member of the Women Divers Hall of Fame, used at 230 msw (751 fsw) a gas mixture of 88% hydrogen, 2% oxygen, balance helium with a slight amount of nitrogen. That 88% hydrogen mixture put the gas mixture well above the 71.3% upper explosion limit for three gas components at 24 bar pressure. The resulting PO2 was 0.5 ata.

Compagnie Maritime d’Expertises (COMEX)

COMEX and their human-rated hyperbaric chambers are located in Marseilles, France.

When it came to manned hydrogen diving, the effect of hydrogen narcosis forced COMEX to operate below the upper explosion limit during its long series of experimental hydrogen dives.

In 1985, COMEX’s Hydra V was the first manned hydrogen dive to 450 msw. Hydrogen fraction was 54%, helium fraction was 45%, and oxygen fraction 1%. PO₂ was a nominal 0.45 atm, the same partial pressure used by the U.S. Navy for saturation dives.

In 1988 during Hydra VIII, the first open water hydrogen dive, the depth was 534 msw, or 1752 fsw. Hydrogen fraction was 49%, helium fraction was 50%, and oxygen fraction 1%. The resulting oxygen partial pressure was 0.54 atmospheres.

The following video documents the record-breaking Hydra VIII dive.

The 534 msw Hydra VIII depth record was broken by Hydra X, a 701 msw, 2300 fsw chamber dive. The gas mixture was the same as in Hydra VIII, hydrogen fraction 49%, helium 50%, and oxygen percentage 1%. Due to the increase in depth, PO₂ rose to 0.7 atm, an oxygen partial pressure frequently used in older U.S. Navy rebreathers.

The head of the Diving Medicine Department at NMRI, CAPT Ed Flynn, M.D. (glasses and grey hair sitting on the right side of the console), was performing physiological studies on both Hydra VI and VIII. In essence he was the Patron Saint of the NMRI Hydrogen Research Facility.

Shallow Hydrogen Diving

What have the previous studies taught us? Well, for one thing, the Swedes showed in their Arne Zetterström Memorial dive that you can get away with oxygen concentrations close to normoxia, PO₂~0.21 ata. The disadvantage of normal atmospheric partial pressures of oxygen, compared to higher pressures, is related to decompression time. There is a decompression advantage when breathing oxygen pressures of 1.3 to 1.45 ata. Virtually all modern electronic rebreathers use those oxygen pressures for that reason. But as the KTH Dive Club showed, hydrogen decompression can be safely handled at relatively shallow depths.

For recreational divers, there is an economic advantage for reducing helium usage by substituting nitrogen. We don’t yet know what the economic and safety comparison would be when using helium diluted hydrogen versus pure hydrogen.

Hydrogen, helium, and oxygen were the standard gases used by COMEX. But they were likely chosen to lessen hydrogen toxicity. Hydrogen toxicity would not be a problem at shallow depth. And in fact, the KTH Dive Club reported no toxicity problems.

Retrospection

As proud as I have been of the record-breaking COMEX hydrogen research program, and of the highly imaginative U.S. Navy hydrogen research program, it has not been lost on me that the first deep human hydrogen dives were conducted by an undoubtedly low-cost program led by a single Swedish Naval Officer, Arne Zetterström.

Now, I find it remarkable that the people testing hydrogen diving at relatively shallow depths, would also be Swedish. Unlike the COMEX and NMRI projects described above, I suspect the KTH Dive club was not sponsored by multimillion dollar programs.

You have to admire the Swedish chutzpah.

Disclaimer: The author is no longer employed by the Navy or Department of Defense. All opinions are my own, and not those of any government agency. This document is posted purely for historical and educational interest. At risk of violent death, under no circumstances should the reader be tempted to explore the production, storage, or use of hydrogen without thorough and certified safety training.

Authorized for Cold Water Service: What Divers Should Know About Extreme Cold

The following is reprinted from my article published in ECO Magazine, March 2015. It was published in its current format as an ECO Editorial Focus by TSC Media. Thank-you Mr. Greg Leatherman for making it available for reprinting.

It is the highpoint of your career as an environmentally minded marine biologist. The National Science Foundation has provided a generous grant for your photographic mission to the waters 100 ft below the Ross Ice Shelf, Antarctica. Now you’re on an important mission, searching for biological markers of climate change.

Under Antarctic Ice, photo by Dr. Martin Sayer.

Above you lies nothing but a seemingly endless ceiling of impenetrable ice, 10 ft thick. Having spent the last several minutes concentrating on your photography, you look up and notice you’ve strayed further from safety than you’d wanted. The strobe light marking the hole drilled in the ice where you’ll exit the freezing water is a long swim away. And, unfortunately, your fellow scientist “buddy” diver has slipped off somewhere behind you, intent on her own research needs.

You’re diving SCUBA with two independent SCUBA regulators, but in the frigid cold of the literally icy waters, you know that ice could be accumulating within the regulator in your mouth. At the same time, a small tornado of sub-zero air expands chaotically within the high-pressure regulator attached to the single SCUBA bottle on your back—and that icy torrent is increasingly sucking the safety margins right out of your regulator. You are powerless to realize this danger or to do anything about it.

At any moment, your regulator could suddenly and unexpectedly free flow, tumultuously dumping the precious and highly limited supply of gas contained in the aluminum pressure cylinder on your back. You’re equipped and trained in the emergency procedure of shutting off the offending regulator and switching to your backup regulator, but this could also fail. It’s happened before.

As you try to determine your buddy’s position, you’re feeling very lonely. You realize the high point of your career could rapidly become the low point of your career—and an end to your very being.

The preceding is not merely a writer’s dramatization. It is real, and the situation could prove deadly—as it has in far less interesting and auspicious locations. Regulator free flow and limited gas supplies famously claimed three professional divers’ lives in one location within a span of one month.

There is a risk to diving in extreme environments. However, the U.S. Navy has found that the risk is poorly understood, even by themselves—the professionals. If you check the Internet SCUBA boards, you constantly come across divers asking for opinions about cold-watersafe regulators. Undoubtedly, recent fatalities have made amateur divers a little nervous—and for good reason.

Internet bulletin boards are not the place to get accurate information about life support safety in frigid water. Unfortunately, the Navy found that manufacturers are also an unreliable source. Of course, the manufacturers want to be fully informed and to protect their customers, but the fact remains that manufacturers test to a European cold-water standard, EN 250. By passing those tests, manufacturers receive a “CE” stamp that is pressed into the hard metal of the regulator. That stamp means the regulator has received European approval for coldwater service.

As a number of manufacturers have expensively learned, passing the EN 250 testing standard is not the same as passing the more rigorous U.S. Navy standard, which was recently revised, making it even more rigorous by using higher gas supply pressures and testing in fresh as well as salt water. Freshwater diving in the Navy is rare—but depending on the brand and model of regulator in use, it can prove lethal.

The unadorned truth is that the large majority of manufacturers do not know how to make a consistently good Performing cold-water regulator. Perhaps the reason is because the type of equipment required to test to the U.S. Navy standard is very expensive and has, not to date, been legislated. Simply, it is not a requirement.

Some manufacturers are their own worst enemy; they cannot resist tinkering with even their most successful and rugged products. This writer is speculating here, but the constant manufacturing changes appear to be driven by either market pressures (bringing out something “new” to the trade show floor) or due to manufacturing economy (i.e., cost savings). The situation is so bad that even regulators that once passed U.S. Navy scrutiny are in some cases being changed almost as soon as they reach the “Authorized for Military Use” list. The military is struggling to keep up with the constant flux in the market place, which puts the civilian diver in a very difficult position. How can they—or you—know what gear to take on an environmentally extreme dive?

My advice to my family, almost all of whom are divers, is to watch what the Navy is putting on their authorized for cold-water service list. The regulators that show up on that list (and they are small in number) have passed the most rigorous testing in the world.

Through hundreds of hours of testing, in the most extreme conditions possible, the Navy has learned what all SCUBA divers should know:

• Even the coldest water (28°F; -2°C) is warm compared to the temperature of expanding air coming from a first stage regulator to the diver. There is a law of physics that says when compressed air contained in a SCUBA bottle is expanded by reducing it to a lower pressure, air temperature drops considerably. It’s the thermal consequence of adiabatic (rapid) expansion.

• Gas expansion does not have to be adiabatic. Isothermal (no temperature change) expansion is a process where the expansion is slow enough and heat entry into the gas from an outside source is fast enough that the expanded gas temperature does not drop.

• The best regulators are designed to take advantage of the heat available in ice water. The most critical place for that to happen is in the first stage where the greatest pressure drop occurs (from say 3,000 psi or higher to 135 psi above ambient water pressure (i.e., depth). They do that by maximizing heat transfer into the internals of the regulator.

• First stage regulators fail in two ways. The most common is that the first stage (which controls the largest pressure drop) begins to lose control of the pressure being supplied to the second stage regulator, the part that goes into a diver’s mouth. As that pressure climbs, the second stage eventually can’t hold it back any longer and a free flow ensues.

• The second failure mode is rare, but extremely problematic. Gas flow may stop suddenly and completely, so that backup regulator had better be handy.

• Second stage regulators are the most likely SCUBA components to fail in cold water due to internal ice accumulation.

• Free flows may start with a trickle, slowly accelerating to a torrent, or the regulator may instantly and unexpectedly erupt like a geyser of air. Once the uncontrolled, and often unstoppable free flow starts, it is self-perpetuating and can dump an entire cylinder of air within a few minutes through the second stage regulator.

• A warm-water regulator free flow is typically breathable; getting the air you need to ascend or to correct the problem is not difficult. In a cold-water-induced free flow, the geyser may be so cold as to make you feel like you’re breathing liquid nitrogen and so forceful as to be a safety concern. Staying relaxed under those conditions is difficult, but necessary.

• Water in non-polar regions can easily range between and 34°F to 38°F; at those temperatures, gas entering the second stage regulator can be at sub-freezing temperatures. European standard organizations classify ~10°C (50°F) as the cold/non-cold boundary. The Navy has found in the modern, high-flow regulators tested to date that 42°F is the water temperature where second stage inlet temperature is unlikely to dip below freezing.

• The small heat exchangers most manufacturers place just upstream of the second stage is ineffective In extreme conditions. They quickly ice over, insulating that portion of the regulator from the relative warmth of the surrounding water.

• Regulator “bells and whistles” are an unknown and can be problematic. Second stage regulators with multiple adjustments can do unpredictable things to heat transfer as the diver manipulates his controls. The last thing a cold-water diver should want is to make it easier to get more gas. High gas flows mean higher temperature drops and greater risk of free flow.

• Only manufacturer-certified technicians should touch your regulator if you’re going into risky waters. The technician at your local dive shop may or may not have current and valid technician training on your particular life support system. Don’t bet your life on it— ask to see the paperwork.

• Follow Navy and Smithsonian* guidance on handling and rinsing procedures for regulators in frigid waters. A single breath taken above the surface could freeze a regulator before you get your first breath underwater.

U. S. Navy reports on tested regulators are restricted. However, the list of those regulators passing all phases of Navy testing is available online. If your regulator, in the exact model as tested, is not on that list, do yourself a favor and don’t dive in frigid waters.

The original Editorial Focus article is found in the digital version of the March ECO magazine here, on pages 20-25.