EXPERT REACTION: ‘Phantom chemical’ in drinking water revealed decades after its discovery

November 21, 2024 in News by RBN Staff

 

RBN Note: 

Dr. Winn Parker, long-time RBN host of Parker’s Pathways, talked about the danger of chloramine for many years on his show… 

It appears that ‘science’ is finally catching up. 


Source: SciMex.org

Publicly released: Fri 22 Nov 2024 at 0600 AEDT | 0800 NZDT
Peer-reviewed: This work was reviewed and scrutinised by relevant independent experts.

International researchers have figured out the makeup of a “phantom chemical” found in some drinking water, over 40 years after it was first discovered. The researchers say US drinking water treated with inorganic chloramines – a treatment also common in Australian drinking water –  contains by-products of the treatment process, and one such by-product has remained unidentified for decades. With help from newer technology, the researchers have identified the “unidentified product” as chloronitramide anion, a compound previously unknown to science. While humans have been consuming this compound for decades, the researchers say it’s still important to assess the toxicity of this substance now that they know what it is.

Journal/conference: Science

Research: Paper

Organisation/s: University of Arkansas, USA

Funder: This work was supported by the National Science Foundation (The NSF grant was awarded to J.L.F. only.); ETH-Zurich; and Eawag (sabbatical stipends to J.L.F.).

Media release

From: AAASChloronitramide anion – a newly characterized contaminant prevalent in chloramine treated tap water – prompts toxicological assessment
Science

Many public water systems in the United States use inorganic chloramines to disinfect drinking water, but their decomposition products have long been a mystery. In a new study, researchers report the discovery of chloronitramide anion – a compound whose existence, though not identity, has been known for 30 years. Detected in the tap water of millions of Americans, this compound’s toxicity remains untested, prompting calls for immediate toxicological evaluation and raising questions about the safety of chloramine in public water supplies.

For over a century, chemical disinfection of public water supplies has effectively reduced waterborne disease by killing pathogens in drinking water. Inorganic chloramines, like monochloramine (NH22Cl) and dichloramine (NHCl2), have become widely used in the U.S. for this purpose and are used to treat the tap water of nearly one-third Americans. However, for decades, chloramine decomposition has been suspected of producing elusive chemical by-products, including potential nitrogen-containing compounds with unknown toxicity. One such disinfection by-product, referred to simply as an “unidentified product”, remains uncharacterized despite being first identified more than 40 years ago.

By combining classic synthesis methods with advanced analytical techniques like high-resolution mass spectrometry and nuclear magnetic resonance (NMR) spectroscopy, Julian Fairey and colleagues isolated and identified chloronitramide anion (Cl–N–NO2-) as a previously unidentified product of inorganic chloramine decomposition.

Fairey et al. measured chloronitramide anion content in a range of chloraminated water systems in the U.S., detecting levels as high as ~100 micrograms per liter (μg/l), which surpasses the typical regulatory limits for many disinfection by-products (60–80 μg/liter). Notably, this compound was absent in water systems that used alternative disinfectants.

Although direct toxicological studies have not yet been conducted, the authors caution that computational analyses suggest that chloronitramide anion may not be benign, emphasizing the need for an immediate toxicological assessment and quantification in source waters, finished drinking waters, and wastewater effluents.

“The findings of Fairey et al. may trigger a reevaluation of the wisdom of chloraminating public water supplies,” writes Daniel McCurry in a related Perspective.

“Regardless of whether chloronitramide anion is found to be toxic or not, its discovery warrants a moment of reflection for water researchers and engineers.”

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Expert Reaction

These comments have been collated by the Science Media Centre to provide a variety of expert perspectives on this issue. Feel free to use these quotes in your stories. Views expressed are the personal opinions of the experts named. They do not represent the views of the SMC or any other organisation unless specifically stated.

Stuart Khan is Professor and Head of School of Civil Engineering at the University of Sydney.

“Chemical disinfection of drinking water is an extremely important practice, and one that has prevented millions of illnesses and premature deaths. It is most certainly among the most impactful public health interventions of the last century. It is well known that all chemical disinfectants, including chlorine and chloramines, lead to the production of disinfection byproducts. It is also widely accepted that we don’t know the precise identity of all disinfection byproducts that are formed. Chloronitramide anion is one such disinfection byproduct which has not, until now, been specifically identified. This research provides us with a little more of the full picture of disinfection byproducts formed following chloramine disinfection of drinking water. Knowing the identity is helpful since it will enable future research aimed at minimising or controlling the formation of disinfection byproducts.

While the precise identity of this disinfection byproduct is new information, it doesn’t change what we know about the safety of chlorinated or chloraminated drinking water. Many studies have been undertaken to directly assess the toxicity of drinking water samples, and these have been undertaken using methods that do not require the identity of specific chemical substances to be known. While there are almost always low levels of toxicity associated with any reactive chemicals, chlorinated and chloraminated drinking water have been shown to be extremely safe when treated in accordance with Australian and international guidelines and standards.

Chloramination is an important drinking water disinfectant, used in several Australian cities. In some systems, it has certain advantages over the other most common disinfectant, chlorine. The most important advantage of chloramination is chemical stability, which means that the quality of the drinking water is protected all the way from the water treatment plant to the customer tap, even over long distances or travel times.”

Last updated: 21 Nov 2024 11:51am
Declared conflicts of interest:

Stuart is a past (non-current) member of the Water Quality Advisory Committee (WQAC) to the National Health and Medical Research Council (NHMRC). This is the committee that oversees and updates the Australian Drinking Water Guidelines (ADWG), which describe practices for the safe treatment and disinfection of drinking water in Australia. He is also a member of the Australian Water Association (AWA).

Professor Ian Rae is an expert on chemicals in the environment at the School of Chemistry at the University of Melbourne. He was also an advisor to the United Nations Environment Programme on chemicals in the environment and is former President of the Royal Australian Chemical Institute

“This is a wonderful bit of chemical detective work. It’s long been known that there is an imbalance between the substances that go into water disinfection with chloramine, and those known to be present in the treated water.

Something was missing. A phantom substance. Now the books have been balanced and the phantom has been revealed as a new substance, hitherto unknown to science. It’s a negatively charged particle consisting of one chlorine atom, two nitrogen atoms and two oxygen atoms. Who would have thought that such a simple combination would have remained undiscovered over several centuries of chemical research in which tens of thousands of chemicals have been put on the books, so to speak?

The deep background to this story is a reminder that chlorine is a rogue element. We use it in a number of ways, but it’s very hard to control and it has a history of ‘getting off the leash’.

Used as chlorine gas, Cl2, it’s a very effective disinfectant – killing bacteria, fungi and other organisms – and it is reactive enough to destroy other chemicals, hence its use as a bleach. If chlorine is added to contaminated water, it mops up the contaminants and forms substances like chloroform. If there is any bromide in the water, it is converted to elemental bromine, which itself forms impurities like bromoform.

The use of the gas in warfare is notorious – a rogue element used by rogues!

Ways to keep chlorine on the leash were found, however. For example, by attaching the chlorine atom to oxygen as in hypochlorite, a common household and industrial bleach and disinfectant. Another strategy is to attach the chlorine to nitrogen, to form chloramines, which we don’t find on our shelves at home but are used industrially. Further in that direction, much of the ‘pool chlorine’ we use has chlorine attached to nitrogen in more complex substances.

Back to the recent research. The unusual feature of chloronitramide, and probably one that contributed to it hiding in the shadows for so long, is that it contains a nitro (NO2) group. Where did that come from? Plausibly, it is the result of active chlorine ripping apart substances like ammonia or another chloramine molecule, leaving their nitrogen attached to two oxygens. It’s a process that chemists refer to as ‘oxidation’ but in this case, the driving force is not oxygen, but active chlorine.

Finally, is chloronitramide toxic? We don’t know yet, but you can bet that toxicologists are working hard to find out. It’s not often that they are confronted with a totally new chemical.”

Last updated: 21 Nov 2024 10:50am
Declared conflicts of interest:

None declared.

Oliver Jones is Professor of Chemistry at RMIT University in Melbourne, Australia

“This is a very interesting and detailed study that uses some very elegant chemistry to solve the identity of a previously unknown disinfection by-product. I am quite convinced by their analytical evidence, which is exceptionally thorough, that the unknown compound is indeed the chloronitramide anion (NB: an anion is an atom or molecule with more electrons than protons, thus having an overall negative charge).

The question then becomes whether chloronitramide is of concern or not?

Disinfection by-products are interesting pollutants as they are not present in the original water but rather are formed when chemicals used for disinfection react with organic matter in the water. They have been known about since the 1970s, and the more common ones are carefully monitored, although I have often thought water companies might need to pay more attention to potential new disinfection by-products. I agree that a toxicological investigation of this anion would be useful now that we know its identity, but  I am not overly worried about my tap water. The compound in question is not newly discovered, just newly defined. Its presence in some (not all) drinking waters has been known for over thirty years.

We should remember that the presence of a compound does not automatically mean it is causing harm. The question is not – is something toxic or not – because everything is toxic at the right amount, even water. The question is whether the substance is toxic at the amount we are exposed to. I think here the answer is probably not. Only 40 samples were tested in this study, which is not enough to be representative of all tap water in the USA and the concentration of chloronitramide was well below the regulatory limits for most disinfection by-products in the majority of samples.”

Last updated: 21 Nov 2024 10:49am
Declared conflicts of interest:

Oliver has declared he has no conflicts of interest but has previously conducted research into disinfection by-products in drinking water.