"Zwitterionic" might not be a word you come across every day, but for Professor Patrick Doyle of the MIT Department of Chemical Engineering, it's a word that's central to the technology his group is developing to remove micropollutants from water. Derived from the German word "zwitter," meaning "hybrid," "zwitterionic" molecules are those with an equal number of positive and negative charges.
Devashish Gokhale, a PhD student in Doyle's lab, uses the example of a magnet to describe zwitterionic materials. "On a magnet, you have a north pole and a south pole that stick to each other, and on a zwitterionic molecule, you have a positive charge and a negative charge which stick to each other in a similar way." Because many inorganic micropollutants and some organic micropollutants are themselves charged, Doyle and his team have been investigating how to deploy zwitterionic molecules to capture micropollutants in water.
In a new paper in Nature Water, Doyle, Gokhale, and undergraduate student Andre Hamelberg explain how they use zwitterionic hydrogels to sustainably capture both organic and inorganic micropollutants from water with minimal operational complexity. In the past, zwitterionic molecules have been used as coatings on membranes for water treatment because of their non-fouling properties. But in the Doyle group's system, zwitterionic molecules are used to form the scaffold material, or backbone within the hydrogel - a porous three-dimensional network of polymer chains that contains a significant amount of water. "Zwitterionic molecules have very strong attraction to water compared to other materials which are used to make hydrogels or polymers," says Gokhale. What's more, the positive and negative charges on zwitterionic molecules cause the hydrogels to have lower compressibility than what has been commonly observed in hydrogels. This makes for significantly more swollen, robust, and porous hydrogels, which is important for the scale up of the hydrogel-based system for water treatment.
The early stages of this research were supported by a seed grant from MIT's Abdul Latif Jameel Water and Food Systems Lab (J-WAFS). Doyle's group is now pursuing commercialization of the platform for both at-home use and industrial scale applications, with support from a J-WAFS Solutions grant.
Seeking a sustainable solution
Micropollutants are chemically diverse materials that can be harmful to human health and the environment, even though they are typically found at low concentrations (micrograms to milligrams per liter) relative to conventional contaminants. Micropollutants can be organic or inorganic and can be naturally-occurring or synthetic. Organic micropollutants are mostly carbon-based molecules and include pesticides and per- and polyfluoroalkyl substances (PFAS), known as "forever chemicals." Inorganic micropollutants, such as heavy metals like lead and arsenic, tend to be smaller than organic micropollutants. Unfortunately, both organic and inorganic micropollutants are pervasive in the environment.
Many micropollutants come from industrial processes, but the effects of human-induced climate change are also contributing to the environmental spread of micropollutants. Gokhale explains that, in California, for example, fires burn plastic electrical cables and leech micropollutants into natural ecosystems. Doyle adds that "outside of climate change, things like pandemics can spike the number of organic micropollutants in the environment due to high concentrations of pharmaceuticals in wastewater."
It's no surprise then, that over the past few years micropollutants have become more and more of a concern. These chemicals have garnered attention in the media and led to "significant change in the environmental engineering and regulatory landscape" says Gokhale. In March 2023, the U.S. Environmental Protection Agency (EPA) proposed a strict, federal standard that would regulate six different PFAS chemicals in drinking water. Just last October, the EPA proposed banning the micropollutant trichloroethylene, a cancer-causing chemical that can be found in brake cleaners and other consumer products. And as recently as November, the EPA proposed that water utilities nationwide be required to replace all of their lead pipes to protect the public from lead exposure. Internationally, Gokhale notes the Oslo Paris Convention, whose mission is to protect the marine environment of the northeast Atlantic Ocean, including phasing out the discharge of offshore chemicals from the oil and gas industries.
With each new, necessary regulation to protect the safety of our water resources, the need for effective water treatment processes grows. Compounding this challenge is the need to make water treatment processes that are sustainable and energy-efficient.
The benchmark method to treat micropollutants in water is activated carbon. However, making filters with activated carbon is energy-intensive, requiring very high temperatures in large, centralized facilities. Gokhale says approximately "four kilograms of coal are needed to make one kilogram of activated carbon, so you lose a significant amount of carbon dioxide to the environment." According to the World Economic Forum, global water and wastewater treatment accounts for 5 percent of annual emissions. In the U.S. alone, the EPA reports that drinking water and wastewater systems account for over 45 million tons of greenhouse gas emissions annually.
"We need to develop methods which have smaller climate footprints than methods which are being used industrially today," says Gokhale.
Supportign a "high-risk" project
In September 2019, Doyle and his lab embarked on an initial project to develop a microparticle-based platform to remove a broad range of micropollutants from water. Doyle's group had been using hydrogels in pharmaceutical processing to formulate drug molecules into pill format. When he learned about the J-WAFS seed grant opportunity for early-stage research in water and food systems, Doyle realized his pharmaceutical work with hydrogels could be applied to environmental issues like water treatment. "I would never have gotten funding for this project if I went to the NSF [National Science Foundation], because they would just say, 'you're not a water person.' But the J-WAFS seed grant offered a way for a high-risk, high-reward kind of project," Doyle says.
In March 2022, Doyle, Gokhale, and MIT undergraduate Ian Chen published findings from the seed grant work, describing their use of micelles within hydrogels for water treatment. Micelles are spherical structures that form when molecules called surfactants (found in things like soap), come in contact with water or other liquids. The team was able to synthesize micelle-laden hydrogel particles that soak up micropollutants from water like a sponge. Unlike activated carbon, the hydrogel particle system is made from environmentally friendly materials. Furthermore, the system's materials are made at room temperature, making them exceedingly more sustainable than activated carbon.
Building off the success of the seed grant, Doyle and his team were awarded a J-WAFS Solutions grant in September 2022 to help move their technology from the lab to the market. With this support, the researchers have been able to build, test, and refine pilot-scale prototypes of their hydrogel platform. System iterations during the solutions grant period have included the use of the zwitterionic molecules, a novel advancement from the seed grant work.
