A luminescent sensor developed at Penn State can detect the rare-earth element terbium, from complex environmental samples like acid mine waste. The sensor takes advantage of a protein that specifically binds to rare-earth elements. According to researchers, it could be harnessed to help develop a domestic supply of these rare-earth metals, which are used in smartphones, electric car batteries, and energy-efficient lighting. Terbium, among the rarest of the rare-earth elements, produces the green color in cellphone displays, and is used in solidstate devices. There are a variety of chemical, environmental, and political challenges to obtaining terbium and other rare-earth elements from the environment. Developing new sources of these metals also requires robust detection methods, which poses another challenge; for example, the method of detecting rare-earth elements in a sample — a type of mass spectrometry called ICP-MS — is expensive and not portable. Portable methods, however, are not as sensitive and do not perform well in complex environmental samples, where acidic conditions and other metals can interfere with detection. Acid mine drainage pollution in a stream in Cambria County, Pa. Courtesy of Rachel Brennan, Penn State. “There is not currently a domestic supply chain of rare-earth elements like terbium, but they are actually quite abundant in nontraditional sources in the U.S., including coal byproducts, acid mine drainage, and electronic waste,” said Joseph Cotruvo Jr., assistant professor and Louis Martarano Career Development Professor of Chemistry at Penn State, a member of Penn State’s Center for Critical Minerals, and senior author of the study. “In this study, we developed a luminescence-based sensor that can be used to detect and even quantify low concentrations of terbium in complex acidic samples.” The sensor relies on lanmodulin, a protein that the researchers discovered is nearly a billion times better at binding to rare-earth elements than to other metals. The protein’s selectivity to bind rare-earth elements is ideal for a sensor, as it is most likely to bind to rare earths instead of other metals that are common in environmental samples. To optimize lanmodulin as a sensor for terbium specifically, the researchers altered the protein by adding the amino acid tryptophan to the protein. “Tryptophan is what is called a ‘sensitizer’ for terbium, which means that light absorbed by tryptophan can be passed to the terbium, which the terbium then emits at a different wavelength,” Cotruvo said. “For our purposes, when the tryptophan-lanmodulin compound binds to terbium, we can observe the emitted light, or luminescence, to measure the concentration of terbium in the sample.” The team tested variations of the tryptophan-lanmodulin sensor. It optimized the location of the tryptophan to minimize interference with lanmodulin’s ability to bind to rare-earth elements. The variants provided important insights into the key features of the protein that enable it to bind rare earths with such high selectivity. The team tested the most promising variant to determine the lowest concentration of terbium the sensor could detect in idealized conditions, with no other metals to interfere. Even under highly acidic conditions, like that found in acid mine drainage, the sensor could detect environmentally relevant levels of terbium. “One challenge with extracting rare-earth elements is that you have to get them out of the rock,” Cotruvo said. “With acid mine drainage, nature has already done that for us, but looking for the rare earths is like finding a needle in a haystack. We have existing infrastructure to treat acid mine drainage sites at both active and inactive mines to mitigate their environmental impact. If we can identify the sites with the most valuable rare-earth elements using sensors, we can better focus extraction efforts to turn waste streams into revenue sources.” Next, the researchers tested the sensor in actual samples from an acid mine drainage treatment facility in Pa., an acidic sample with many other metals present and very low levels of terbium — three parts per billion. The sensor determined a concentration in the sample that was comparable to what they detected with the mass spectrometry method. “We plan to further optimize the sensor so that it is even more sensitive and can be used more easily,” Cotruvo said. “We also hope to target other specific rare-earth elements with this approach.” The research was published in the Journal of the American Chemical Society (www.doi.org/10.1021/jacs.1c06360).