Monday, October 9, 2023

The Real Water Case: Is it possible to make hydrazine from molecular nitrogen and electricity?

Some of you may remember the "Real Water" case from 2021, where 6 people were sickened by drinking water: 

LAS VEGAS (AP) — Federal and local health officials are warning people not to drink a Las Vegas-based bottled water brand, Real Water, after linking it to liver illness in five hospitalized children.

Company President Brent Jones on Wednesday called for stores to stop selling the product “throughout the United States until the issue is resolved.” “Our goal is to diligently work with the FDA to achieve a swift resolution,” a statement from Jones said.

The U.S. Food and Drug Administration warned consumers, restaurants and retailers not to drink, cook with, sell or serve the product, the Southern Nevada Health District said in a statement posted Tuesday.

...The health district, based in Las Vegas, said it began investigating five cases of acute non-viral hepatitis in November 2020 and notified the FDA. It said it also investigated the illness of six other people — three children and three adults — who reported less severe symptoms including vomiting, nausea, appetite loss and fatigue.

Five children required hospitalization but recovered, the health district said. The patients lived in four different households.

Well, it looks like a jury has ruled against Real Water (article by Beth Mole): 

A jury this week awarded $228.5 million to seven plaintiffs in their case against Nevada-based water company Real Water, which sold alkaline water tainted with hydrazine, a highly toxic chemical found in fuel for rockets and spacecraft.

The plaintiffs included a 7-month-old boy who was hospitalized with severe liver failure and nearly needed a liver transplant. Another was a 69-year-old woman who was hospitalized for liver failure after drinking the water for years. She died in the hospital on November 11, 2020.

What is strange is what chemical they suggested was to blame: 

As federal regulators began investigating the company's water, they found a troubling water treatment process.

According to the DOJ's 2021 complaint and testimony in the trial over the last few weeks, Real Water processed municipal tap water "by carbon filtration, reverse osmosis filtration, ultraviolet light filtration, and ozone filtration." Then potassium chloride is added and the water goes through a proprietary "ionizer" apparatus to apply an electrical current to the water. This allegedly created positively charged and negatively charged solutions. Real Water employees would discard the positively charged solution and keep the negatively charged solution.

That initial batch of negatively charged solution would then go though the "ionizer" apparatus and be separated again. The resulting negatively charged solution would then be treated with potassium hydroxide (a form of lye), potassium bicarbonate (sometimes used in baking powders), and magnesium chloride (a salt used in nutritional supplements and for de-icing roads); this formed an "E2 concentrate" product, which, when diluted, formed their alkaline water product.

The FDA identified hydrazine in product samples it tested. In the trial, Issam Najm, an environmental engineer who specializes in water chemistry and testing, testified that the hydrazine likely formed in the "ionizer," which was just titanium tubes electrified with what looked like jumper cables used to charge a car battery. Najm testified that, in the charged water, nitrogen gas naturally found in air could have reacted with water to form hydrazine (N2H4), or, during the electrolysis, ammonia (NH3) was formed first, before reacting with hydroxide to form hydrazine.

Reader, does this make sense to you? First (unfortunately), we do not have a link for how the FDA determined that hydrazine was present. But I am really under the impression that it is not easy to make hydrazine or ammonia (to make hydrazine), especially from molecular nitrogen. Don't you have to have some kind of reductant? (Where is the hydrogen ion coming from?) Does anyone have a viable mechanism? I am genuinely skeptical, but gee, I dunno. Anyone else? 

5 comments:

  1. Very cool article! I am an electrochemist, I don't see this reaction happening at all under typical conditions. If we were to investigate if it really is possible, then we need to know what is in the electrode, down to ppm level of dopant, what is in the electrolyte, again down to ppm level, and how much voltage was applied. These are just starting questions...

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  2. Not an electrochemist, but it would indeed be interesting to know the details of the FDA analysis. I don't know what levels of hydrazine are involved, but in my career in industrial chemistry, it was always a tour de force to look at the source of trace impurities that led to anything from undesirable colors and odors to poisoned catalysts. Since they were generally present at ppm levels, "textbook" synthetically useful chemistry and mechanisms were often not of much use in determining where they came from.

    And why the heck are people giving "alkaline water" to 7 month olds? I know it's supposed to be a health thing, but experiment on yourself and not on some poor kid.

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  3. I am not very good at nitrogen chemistry but a quick look at a reference book shows that ammonia has been made experimentally with nitrogen and water in the presence of a titanium oxide catalyst and solar energy. Something similar could have happened so I guess it is possible that the ammonia could then react with the hypochlorite in the municipal water they used (assuming the carbon and revers osmosis filtration was not really used) to make chloroamine, more ammonia and base should get you hydrazine.

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    1. huh that's fascinating

      they certainly had enough base

      I have a real sense that they did not exactly have a controlled, documented process, but I dunno

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  4. I wonder if there was chloramine present in the water to begin with? Swimming pools are known to have chloramine in them, formed by reaction between the chlorinator and "organic" nitrogen compounds (you can imagine what that means). This might be a stretch, but if the municipal water source is a reservoir, also used for recreation, it seems conceivable that the water could likewise end up with chloramines created during treatment. I don't think this explains the source of ammonia required to finish off the sequence to hydrazine, though.

    Also, it was mentioned that KCl was added to water before "ionization" - if I remember correctly, chloride oxidation has a lower overpotential than water oxidation, so it seems hypochlorite might be generated during the first "ionization" step.

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looks like Blogger doesn't work with anonymous comments from Chrome browsers at the moment - works in Microsoft Edge, or from Chrome with a Blogger account - sorry! CJ 3/21/20