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The article link is available here: Inside the Laboratory: The Blaney Laboratory at the University of Maryland Baltimore County (chromatographyonline.com)

"Inside the Laboratory" is a series in collaboration with LCGC and Spectroscopy, highlighting the pioneering work of analytical scientists worldwide. In this edition, we delve into the groundbreaking research of Dr. Lee Blaney from the University of Maryland, Baltimore County (UMBC). Dr. Blaney, a Professor and Associate Director of Sustainability Engineering, leads his team in developing advanced methods using liquid chromatography (LC) techniques to analyze contaminants of emerging concern (CECs) in environmental samples.

Environmental analysis is a field where chromatography plays an integral role. Detecting, identifying, and quantifying per- and polyfluoroalkyl substances (PFAS) and contaminants of emerging concern (CECs) are currently hot topics in environmental analysis, mostly because it affects both the environment and natural resources humans regularly use. Chromatographic techniques like liquid chromatography coupled to tandem mass spectrometry (LC–MS/MS) offer unparalleled sensitivity and specificity in separating and identifying PFAS within complex matrices, such as water, soil, and biological samples. Through chromatographic separation, PFAS are eluted based on their unique physicochemical properties, allowing accurate and precise quantification by downstream detectors. This analytical approach not only aids in assessing environmental contamination, but also contributes significantly to understanding the exposure pathways and potential health risks associated with PFAS.

Dr. Lee Blaney is a Professor and Associate Director of Sustainability Engineering at the University of Maryland Baltimore County. He received his BS and MS in Environmental Engineering at Lehigh University before completing his PhD in Civil Engineering at the University of Texas at Austin. His laboratory is primarily focused on studying CECs, including developing advanced analytical methods that can better improve detection and quantification of CECs in the environment, as well as developing new treatment technologies for diverse contaminants in water and wastewater.

Aerial view of University of Maryland Baltimore County UMBC Catonsville | Image Credit: © vitanovski - stock.adobe.com

Recently, LCGC International spoke to Dr. Blaney about his laboratory’s work with PFAS and CEC analysis, as well as the current research projects they are working on.

Dr. Lee Blaney of the University of Maryland, Baltimore County | Photo Credit: © Lee Blaney

Can you tell me about the research that your laboratory group is working on currently?

Most of our research involves contaminants of emerging concern (CECs), such as pharmaceuticals, hormones, and personal care products. These are chemicals that we use every day to improve our quality of life, but we don’t really think about them as “pollution." Nevertheless, every chemical that we use ultimately makes its way into the aquatic environment, where it can have unintended consequences. When we take an antibiotic to fight an infection, some fraction of the antibiotic gets excreted into our toilets without undergoing any chemical changes. Wastewater treatment plants were not designed to remove pharmaceuticals, causing antibiotics to be discharged into the environment, where they can accelerate the development and spread of antimicrobial resistance. Similar concerns abound for other CECs. For this reason, our group focuses on developing (i) new analytical methods to measure CECs in the aquatic environment and (ii) new treatment technologies to ensure CEC removal from both drinking water and wastewater.

Blaney (left) with undergraduate researcher Ouriel Ndalamba (center) and PhD candidate Jahir Antonio Batista-Andrade (right) discuss an LC-MS/MS method for CEC measurement in Baltimore streams. Photo Credit: © Lee Blaney

In the research that you and your group does, what particular analytical techniques do you normally use?

Our laboratory primarily employs liquid chromatography (LC) coupled to ultraviolet (UV), fluorescence (FL), and triple quadrupole tandem mass spectrometry (MS/MS) detectors. Some CECs have strong absorbance and/or fluorescence properties that allow us to measure their concentrations using high performance liquid chromatography (HPLC) with UV or FL detection in relatively clean samples, such as those produced during laboratory experiments. However, real environmental samples contain dozens of CECs at concentrations of 1–1000 ng/L (that is, 1–1000 parts per trillion). Real samples also contain much higher concentrations of natural organic matter and background ions. With appropriate pretreatment via solid-phase extraction, we can not only concentrate the analytes, but also remove some of the interfering substances. Nevertheless, the large number of CECs in real samples mandates the use of LC–MS/MS, which can concurrently measure analytes with similar retention times. During LC–MS/MS analysis, we have several analytical criteria that ensure highly selective and sensitive measurement of each CEC. In particular, we need to match the LC retention time of our chemical standards for each CEC, produce the same MS-1 ion during electrospray ionization, and generate the same MS-2 ions for analyte quantitation and confirmation by the triple quadrupole MS/MS detector. The fast scan times of the MS/MS detector allow us to measure dozens of CECs in the same method. These aspects make LC–MS/MS the go-to technology for environmental analytical chemists and engineers studying CECs.

Blaney (second from left) with undergraduate researchers Bridget Anger (left) and Lauren Harris (right) and PhD candidate Mamatha Hopanna (second from right) discuss photochemical treatment of antibiotics in water. Photo Credit: © Lee Blaney

What’s the difference between CECs and PFAS?

Contaminants of emerging concern is an umbrella term for all contaminants that have been identified as having potentially harmful effects on the environment or humans. The “emerging” concern means that we do not yet fully understand the toxicity of these chemicals in the environment or people. Per- and polyfluoroalkyl substances (PFAS) are a class of almost 15,000 fluorinated chemicals used in fire-fighting foams, nonstick cookware, fast food wrappers, and many other industrial and consumer products. Even though there are many PFAS, you can consider them to be a subcategory of CECs. Due to the chemical and thermal stability of the carbon-fluorine bonds in PFAS, these chemicals do not readily degrade during wastewater treatment or in the environment. In the last few years, we have learned about a number of harmful outcomes of PFAS in humans. As a result, new drinking water regulations were recently approved for six PFAS in drinking water. In a sense, some PFAS have therefore transcended the concept of “contaminants of emerging concern” and have just become “regulated contaminants." The new regulations for PFAS will also spur the growth and development of analytical contract labs to meet the demand for regular analysis of PFAS in drinking water across the country.

Going back to LC–MS methodologies, are there any limitations of using that technique right now that are kind of preventing you and your group from figuring some things out in your research or?

The biggest limitation is the large number of CECs. Right now, we are only measuring a small fraction of the specialty chemicals employed in everyday life. For example, our lab has developed methods for dozens of antibiotics, but each of those compounds undergo chemical transformations in natural and engineered systems. These reactions produce several unknown transformation products that may still retain antimicrobial properties. Without chemical standards, it is difficult to employ targeted LC–MS/MS methods to measure these transformation products. As another example, the latest EPA method measures 40 PFAS, which accounts for less than 1% of the estimated 15,000 PFAS. If we extrapolate this issue across the full suite of CECs, the number of individual chemicals becomes staggering. For this reason, we have prioritized certain chemicals that represent the most concern, but new approaches will be needed in the future to best safeguard environmental and public health.

Blaney (right) with undergraduate researchers Fabian Amurrio (left) and Lauren Harris (second from right) and PhD candidate Utsav Shashvatt (second from left) discuss ion chromatography results related to a project focused on nutrient recovery from waste streams. | Photo Credit: © Lee Blaney

With all the advancements that are going on in with the techniques and the technologies, how does you and your group stay on top of all the developments going on in this space?

We regularly go to conferences and meetings focused on the latest developments in CEC analysis. Several of our current projects are funded by the Strategic Environmental Research and Development Program (SERDP), which holds regular meetings for PFAS-related research. These conferences and meetings are great opportunities to share our work, receive feedback, learn about the work of other groups, and share notes to advance knowledge in the environmental analytical chemistry and environmental engineering fields. In addition, I serve as an executive editor at the Journal of Hazardous Materials. While it is a demanding job to keep up with all the manuscripts submitted by authors, this role also gives me a chance to read the latest work from around the world to learn about the latest updates and findings.

Are there any upcoming research projects on your end that you’re excited about?

Our best available technologies for PFAS treatment work well for long-chain PFAS, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), which contain eight carbon atoms in their chemical structures. Short- and ultrashort-chain PFAS, which contain less than eight carbons, pose challenges to conventional treatment technologies. Many of these compounds are also not included in current analytical methods. Our new SERDP project will focus on developing novel hybrid anion-exchange resins to remove these challenging contaminants from water. We’re excited about our materials and the promising preliminary data, and we’ll look forward to sharing our findings with the environmental community to continue to address the challenges associated with PFAS treatment and remediation.

This interview has been edited for clarity.

About the Interviewee

Lee Blaney, PhD, is a Professor and Associate Director of Sustainability Engineering at the University of Maryland Baltimore County.

Dr. Tyler R Josephson, Assistant Professor, Chemical, Biochemical, and Environmental Engineering department at the University of Maryland, Baltimore County, along with UMBC student and alumni, Charles Fox, Neil D Tran, F Nikki Nacion, and Samiha Sharlin, have a new publication in Machine Learning: Science and Technology titled "Incorporating background knowledge in symbolic regression using a computer algebra system."

The article is available here:
Incorporating background knowledge in symbolic regression using a computer algebra system - IOPscience

DOI 10.1088/2632-2153/ad4a1e

Abstract:

Symbolic regression (SR) can generate interpretable, concise expressions that fit a given dataset, allowing for more human understanding of the structure than black-box approaches. The addition of background knowledge (in the form of symbolic mathematical constraints) allows for the generation of expressions that are meaningful with respect to theory while also being consistent with data. We specifically examine the addition of constraints to traditional genetic algorithm (GA) based SR (PySR) as well as a Markov-chain Monte Carlo (MCMC) based Bayesian SR architecture (Bayesian Machine Scientist), and apply these to rediscovering adsorption equations from experimental, historical datasets. We find that, while hard constraints prevent GA and MCMC SR from searching, soft constraints can lead to improved performance both in terms of search effectiveness and model meaningfulness, with computational costs increasing by about an order of magnitude. If the constraints do not correlate well with the dataset or expected models, they can hinder the search of expressions. We find incorporating these constraints in Bayesian SR (as the Bayesian prior) is better than by modifying the fitness function in the GA.

Dr. Ömer Özgür Çapraz, Associate Professor, Chemical, Biochemical, and Environmental Engineering department at the University of Maryland, Baltimore County, published a groundbreaking study in Electrochimica Acta titled "Probing interfacial stress on Au cathode in DMSO electrolyte during electrochemical polarization in aprotic Li-O2 batteries" with collaborators from Oklahoma State University, Bar-Ilan University, National Renewable Energy Laboratory, The Hebrew University of Jerusalem.

The full article is available from ScienceDirect at https://doi.org/10.1016/j.electacta.2024.144522

Abstract:

The practical performance of Li-O2 batteries suffers from interfacial instabilities associated with the reaction intermediates. These instabilities on the cathode-electrolyte interface dictate the direction of the oxygen evolution and reduction reactions (OER/ORR) in Li-O2 batteries. Despite intensive research on chemical instabilities in the reaction intermediates, there is limited work on understanding the importance of stress on the interfacial dynamics. To address this gap, in-situ curvature measurements were conducted to probe interfacial stress generation during electrochemical polarization on Au cathode in DMSO electrolytes. Charge accumulation induces tensile stress, whereas compressive stress generation is associated with the adsorbate-induced stress and mismatch strain between reaction intermediates and the Au surface. Abrupt stress relaxation on the onset of discharge presents evidence for a contribution of electrostriction stress. Adsorption of redox mediator nitrate ions induces compressive stress before ORR. Unique findings demonstrate the impact of interfacial stress on the OER/ORR in Li-O2 batteries.

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The remains of the Francis Scott Key Bridge after a collision with a malfunctioning cargo ship on March 26. (Photo source: Corey Jennings '10, Maryland Comptroller/Flickr)

Examining the environmental impacts of the collapse 

The ship that collided into the bridge was carrying 56 containers of hazardous materials, including corrosives, flammables, and lithium-ion batteries. The cargo ship was also carrying more than one million gallons of fuel at the time of the impact. City officials began their investigations into the incident, which included determining the environmental impacts to the Patapsco River and surrounding communities. 

Upal Ghosh, professor of chemical, biochemical, and environmental engineering, whose research includes examining the effects of toxic pollutants in soils, sediments, and aquatic environments, was among the experts who weighed in on assessing the potentially hazardous effects of the containers that were resting at the bottom of the river. 

Maryland Comptroller Brooke Lierman and representatives of the Office of the Governor take a tour of the Francis Scott Key Bridge collapse site on a Maryland Department of Natural Resources police boat. (Photo source: Corey Jennings ’10, Maryland Comptroller/Flickr)

Ghosh told the Baltimore Sun days after the collapse that environmental officials’ first priority would likely be making sure none of the intact containers were breached.

“If you have containers that contain oily material, those things will, if they are breached, be releasing over time,” Ghosh said. “I would think if there is a release that goes down into the sediments under the water, it would be a local impact right there.” 

Farah Nibbs, assistant professor of emergency and disaster health systems, is also thinking about future ways to contain the effects of similar disasters. Contributing factors to the bridge’s collapse, she says, can be tied to the 2012 expansion and modernization of the Port of Baltimore. Those changes did not happen hand in hand with improvements in safety management needed to accommodate ships of such huge sizes that now were able to port in the city. Risks from collisions, fuel spills, and contamination still lack proper oversight and regulation.

“A novel approach for decision-makers may be to view Maryland’s emergency management and transportation experts and service providers—as well as the physical bridge infrastructure itself—as part of the community’s lifeline systems,” said Nibbs. 

~~

Read the full article: Infrastructure Of Support After Key Bridge Collapse - UMBC: University Of Maryland, Baltimore County

On the first weekend of April, hundreds of chemical engineering students from across the Mid-Atlantic converged on the UMBC campus for two days of learning, networking, and friendly competition. They heard talks from academic and industry leaders, attended workshops and a career fair, competed in rounds of ChemE Jeopardy, mixed chemicals to power small cars along a track in the ChemE Car competition, and mingled over catered lunches, dinners, and cups of evening hot cocoa. 

The activities were all part of the 2024 Mid-Atlantic Student Regional Conference of the American Institute of Chemical Engineers (AIChE)—hosted by the UMBC student chapter of the national group. Around 400 people attended the event, an increase from last year’s conference at Virginia Tech. Organizing the logistics, recruiting speakers and sponsors, securing rooms, and ordering thousands of plates worth of food presented a formidable challenge—one that the UMBC students tackled with aplomb. 

“I am feeling fantastic after the conference,” says Pavan Umashankar ’25, chemical engineering and biochemistry and molecular biology, who served as the chair of the conference organizing committee. “I am super proud of everyone’s commitment and dedication to make it a resounding success.”

“Truly, I could gush about the UMBC conference planning team all day,” says Alyssa Block, the membership associate of ChemE student programs for AIChE. “These students really are the future leaders of their profession and of AIChE: engaged, excited, collaborative, supportive of each other, and willing to lend a hand.” 

A club on the upswing 

Hosting an AIChE regional conference for the first time at UMBC marked a milestone for a student club that has seen increasing levels of engagement and success in recent years. While many college clubs across the country are in decline post-Covid, UMBC’s AIChE student chapter is on a clear upward trajectory. The club sent its first team to compete in ChemE Jeopardy at the spring 2019 AIChE regional meeting. Just three years later, the UMBC team won the national ChemE Jeopardy competition. 

Neha Raikar, a senior lecturer in the Department of Chemical, Biochemical, and Environmental Engineering (CBEE) and one of the advisors to the student AIChE chapter, remembers attending the 2019 meeting: “Back then, we wondered if we would ever be able to host a regional conference at UMBC,” she says. “We’ve achieved that goal.” 

It was especially remarkable, she adds, to see some members of UMBC’s first ChemE Jeopardy and ChemE car teams return to this year’s conference as industry representatives.

Strong attendance and smooth conference logistics weren’t the only successes of the weekend—UMBC also triumphed in the ChemE Jeopardy and ChemE car competitions. 

“Planning for the conference was already a significant undertaking, and on top of that, many of our students participated, and excelled, in the competitions,” says Raikar. “Their achievements not only showcased their individual capabilities but also the strength of our club as a whole, which is growing and thriving.”

A winning formula

AIChE chapter members and their advisors ascribe the club’s success to the hard work and dedication of the students coupled with the support of the CBEE department, college, and university. Thirteen CBEE students formed the conference planning committee, which met regularly to ensure all conference planning efforts were on track. An additional 37 students and 14 faculty and staff also volunteered their time—as check-in staff, poster and presentation judges, and more. About 10 UMBC alumni actively participated in the conference, and others contributed to fundraising efforts, helping the organizing committee secure sponsorships from notable companies such as AstraZeneca, ExxonMobil, Advanced Thermal Batteries, and Astek Diagnostics and from the chemical engineering department of Columbia University. 

An Dang ’24, chemical engineering, led the fundraising efforts. She gamely approached industry representatives at the UMBC career fair and made the pitch. “I’m not an extrovert, and being in these roles forced me to go out of my comfort zone,” she says.

“Securing sponsorships was vital for making the conference possible, and An did a remarkable job” says Mariajosé Castellanos, another CBEE faculty who advises the AIChE chapter. Castellanos also praised the management skills of conference planning committee chair Umashankar. “Despite his modesty, Pavan is a true mastermind in everything he does,” she says.

For their part, the students applauded the support of the CBEE department, especially the work of their two advisors, Raikar and Castellanos, and the event planning support of Andrea Miller, the CBEE graduate program coordinator. 

The conference was both a marker of the club’s success and an opportunity for individual students to grow their skill sets.

“I have developed leadership and project management skills, which will be incredibly useful throughout my professional career,” says Umashankar. 

Ben Welling ’25, chemical engineering, the leader of the UMBC ChemE car team, believes his experience with the competition helped him land internships. “I talked about it extensively with employers. They like leadership experience and it shows you are willing to do more than is required.” 

Raikar sees a bright future for the student stars of this year’s conference and for the club as a whole. “I hope the conference will boost the club membership and participation of students in other AIChE activities,” she says. And, she adds, the conference shows that with support, “UMBC students can accomplish any task.”

Congratulations Dr. Gautom Das on the successful promotion to the rank of Senior Lecturer!