Archive for May, 2019

On the importance of considering all reaction partners: a lesson from birnessite-induced BPA oxidation

Bisphenol A (BPA) is one of the most used industrial chemicals worldwide. Since its introduction in the market in 1959, BPA production has increased steadily and it is forecasted to reach 7.3 million tons by the end of 2023.1 BPA is used for a range of applications: from dental sealants to internal can coatings, electronic equipment and supermarket receipts.2 “In the past years, concerns have been raised over the use of this compound due to its estrogenic effects that can be observed also at low BPA concentration, such as the ones found in the natural environment.2,3 Thus, investigation of natural attenuation processes might help us developing strategies to reduce human exposure to this widespread chemical.

Several literature studies showed that manganese oxides (MnOx)-mediated oxidation represents the main PBA degradation pathway in anoxic conditions.2 This process produces a series of degradation products, including radicals that might couple to dissolved organic matter to form the so-called “bound residues”, unknown high molecular weight products whose long-term environmental risks are still debated.4 A detailed knowledge of the reaction mechanism will therefore allow to predict, and ideally prevent, the formation of degradation products that might be more hazardous than the parent compound.

In this context, Balgooyen et al. used stirred flow reactors to investigate the effect of influent concentrations on BPA degradation mechanism via birnessite (δ-MnO2) oxidation. This research question was motivated by the hypothesis that higher influent concentrations might lead to a higher formation of bound residues. The results of this work are directly relevant for engineered water treatment systems that use MnOx-coated sand,5 where contaminant inflow concentrations might change during time.

As a unique feature of this work, the authors used a combined approach based on the detection of both organic and inorganic reaction products. Specifically, they followed the formation of both hydroxycumil alcohol (HCA) and aqueous Mn(II). HCA is the main PBA oxidation product and is considered a proxy for bound residues formation, while Mn(II) is a reaction byproduct released in solution upon reduction of birnessite.

Unexpectedly, the two approaches gave opposite results: HCA yields were constant for the influent concentration range investigated, while Mn(II) yields decreased as the influent concentration increased. In order to explain their results, the authors hypothesized that Mn(II) was not an accurate proxy, as comproportionation and disproportionation reactions occurring at the mineral surface might alter aqueous Mn(II) concentrations. Using an elegant series of sorption and desorption experiments, Balgooyen et al. were able to confirm this hypothesis, leading to the conclusion that BPA oxidation mechanism in stirred-flow reactors is indeed independent from the influent concentration.

In addition to providing a valuable new piece of information for the complex puzzle of BPA cycling in anoxic conditions, the work of Balgooyen et al. teaches us something that has little to do with micropollutants or flow-through reactors: for a throughout study of a chemical mechanism, all reaction partners must be considered – no matter how many different analytical techniques you will have to use.

To download the full article for free*, click the link below:

Impact of bisphenol A influent concentration and reaction time on MnO2 transformation in a stirred flow reactor

Sarah Balgooyen, Gabrielle Campagnola, Christina K. Remucal and Matthew Ginder-Vogel

Environ. Sci.: Processes Impacts, 2019, 21, 19

DOI: 10.1039/c8em00451j


About the Webwriter:

Rachele Ossola is a PhD student in the Environmental Chemistry group at ETH Zurich. Her research focuses on photochemistry of dissolved organic matter in the natural environment.

 

 

 


Additional references

(1)        The Global Bisphenol A Market, https://www.researchandmarkets.com/reports/4665281/the-global-bisphenol-a-market (accessed May 26, 2019).

(2)        Im and Löffler, Environ. Sci. Technol. 2016, 50 (16), 8403–8416.

(3)        vom Saal and Hughes, Environ. Health Perspect. 2005, 113 (8), 926–933.

(4)        Barraclough et al. Environ. Pollut. 2005, 133 (1), 85–90.

(5)        Charbonnet et al., Environ. Sci. Technol. 2018, 52 (18), 10728–10736.

 

*Article free to access until the 30th June 2019

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Emerging Investigator Series: Sarah Jane White

Sarah Jane White studies the biogeochemical cycling of metals that are critical in emerging energy technologies but whose environmental behavior and impacts remain largely unknown. She is interested in metal transport and speciation in natural ecosystems, and its intersection with contaminant fate & transport, industrial ecology, and human health. Sarah Jane received her doctoral degree in Environmental Chemistry from MIT, and her bachelor’s degree in Chemistry from Princeton University. She held positions as a Postdoctoral Fellow and Research Associate at the Harvard School of Public Health while doing multidisciplinary research as an NSF Science, Engineering, and Education for Sustainability Fellow. She continued her research and taught in the Environmental Studies Program as a Visiting Associate Research Scholar at Princeton University before joining the U.S. Geological Survey as a Research Chemist in 2017. Presently Sarah Jane’s research focus is the cycling of indium, gallium, and germanium during the mining and processing of zinc ores (of which they are a byproduct), with a goal of understanding the full life cycle of these elements from ore formation, through mining and processing, to their subsequent behavior and potential health impacts when released to the environment.

Read Sarah Jane White’s Emerging Investigator Series article “atmospheric cycling of indium in the northeastern United States” and read more about her in the interview below:

Your recent Emerging Investigator Series paper focuses on atmospheric cycling of indium. How has your research evolved from your first article to this most recent article?

My first published article was about what causes Candida albicans, a typically-benign yeast that everyone has in their bodies, to switch to a virulent form that can cause significant problems in immunocompromised people.  That paper was a result of work that I did as a lab technician – my first job out of college.  After doing an undergraduate thesis in environmental chemistry, and not having taken any biology courses in college, I serendipitously had the opportunity to work in a molecular biology lab, and knew that the opportunity to better understand biology would enhance the environmental science that I was hoping to do in the future.  After that, I went back for a PhD in environmental chemistry, where I focused on contaminant fate and transport – for which biology is immensely important!  As my research interests have expanded even further to include human exposure to metals and subsequent impacts on health, this biology experience has proven invaluable. Now my work focuses on the environmental and anthropogenic cycling of elements like indium, that are critical to new energy technologies but whose environmental behaviors and human health impacts are poorly understood.

What aspect of your work are you most excited about at the moment?

I have recently begun doing some synchrotron-based x-ray absorption work to determine the speciation of germanium in mine wastes.  It has been exciting to learn a new technique that has powerful implications for understanding the mobility, bioaccessibility, and potential for recovery of a critical element from mine wastes.

In your opinion, what are the most important questions to be asked/answered in this field of research?

There are a dizzying number of chemicals and metals that we are exposed to on a daily basis, many of which have poorly characterized toxicity and environmental behavior.  I believe that it is essential for researchers to not only study the behavior and toxicities of these elements and compounds, but also find ways to predict their characteristics to protect human and organismal health.

What do you find most challenging about your research?

Juggling multiple projects at once, and finding sufficient time to invest in all of them.

In which upcoming conferences or events may our readers meet you?

I just returned from a workshop on the environmental behavior of technology-critical elements in Croatia, and don’t have conference travel planned until likely the AGU Fall Meeting in December.

How do you spend your spare time?

I spend most of my non-working time with my husband and two young kids.  We like to go on bike rides, hit wiffle balls in the backyard, play music, garden, go to farmers’ markets…

Which profession would you choose if you were not a scientist?

Baseball radio announcer?  Violin maker?  Physical therapist?

Can you share one piece of career-related advice or wisdom with other early career scientists?

Research is worthless unless people know about it.  For me, this means working to overcome perfectionist tendencies so that my work is published, even if not perfect.

 

 

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Emerging Investigator Series: Shantanu Jathar

Shantanu Jathar is an Assistant Professor in Mechanical Engineering and also an affiliate of the Energy Institute at Colorado State University. He leads the Laboratory for Air Quality Research (http://tinyurl.com/aerosol-csu) that performs research at the intersection of energy and the environment. By leveraging laboratory and field experiments and regional air quality models, his group studies the atmospheric evolution and properties of air pollutants arising from energy and combustion systems, all in the interest of addressing future energy and environmental policy. He has a Ph.D. from Carnegie Mellon University where he used numerical models and laboratory experiments to understand the atmospheric formation of organic aerosols from combustion sources. He worked as a post-doctoral scholar at the University of California, Davis where he worked on improving the treatment of particulate matter in air quality models used for regulatory purposes. Shantanu hails from the suburbs of Mumbai, India. He is married to Poorva (an electrical engineer) and is enjoying parenthood with two energetic sons. In his spare time, he likes to run, bike, hike, and play the bansuri (bamboo flute).

Read his latest Emerging Investigator Series “Oxidative Potential of Diesel Exhaust Particles: Role of Fuel, Engine Load, and Emissions Control” and find out more about him in the interview below:

Your recent Emerging Investigator Series paper focuses on oxidative potential of diesel exhaust particles and the role of fuel, engine load, and emissions control. How has your research evolved from your first article to this most recent article?

My first project, as a graduate student at Carnegie Mellon University nearly a decade ago, examined the influence of an updated treatment on the global distribution of organic fine particles in a climate model. This study was motivated by the need to reduce the large uncertainties linked to fine particles in climate models. Over the years, my research interests have broadened to think about the impacts of fine particles on human health. In this study, we probed how the oxidative reactivity (proxy for toxicity) of particles generated by a modern-day diesel engine varied as we changed the fuel and engine operation. We found that biodiesel and the use of an emissions control device (particle filter) significantly lowered the oxidative reactivity of diesel exhaust particles and we suspect that the reduced oxidative reactivity might be from lower soot emissions. Our work provides some evidence that wider adoption of biofuels and stricter regulations on diesel vehicles may reduce their harmful impacts on human health.

What aspect of your work are you most excited about at the moment?

It has to be wildfires. Wildfires are a growing concern in the western United States as rising temperatures have been linked to more frequent and bigger wildfires. Unlike burning fossil fuels in a controlled environment (think of the internal combustion engine), the variability in fuel and environmental conditions under which fires burn results in large variability in their emissions. As a result, there are large uncertainties surrounding the atmospheric evolution and impacts from wildfire emissions. We have a project supported through the National Oceanic and Atmospheric Administration (NOAA) where we are studying the atmospheric evolution of wildfire emissions in a controlled environmental chamber and using computer models trained on the laboratory data to predict the evolution in real wildfire plumes.

In your opinion, what are the most important questions to be asked/answered in this field of research?

Fine particles when inhaled deposit in our respiratory system and have been linked to lung and cardiovascular disease. However, little is understood about what properties of the particle — defined by their size and composition — are responsible for those diseases and how they might affect different individuals over different periods of time. This, I believe, is an open question and we are not going to figure the answer to this anytime soon.

What do you find most challenging about your research?

Very broadly, I study the sources and impacts of air pollution arising from energy and combustion sources. What I find most challenging with this research area is to keep abreast of the breadth and depth of topic areas it encompasses: physics, chemistry, biology, mathematics, engineering, statistics, public health, and more. Thankfully, the vastness is humbling and I rely on collaborations with some very smart people at Colorado State University and elsewhere to bring their expertise to the topic.

In which upcoming conferences or events may our readers meet you?

I usually don’t miss the annual American Association for Aerosol Research Conference (AAAR), which will be in Portland, OR this year in October. It’s the perfect place to get my scientific fix for fine particle research and catch up with collaborators and colleagues.

How do you spend your spare time?

My wife and I have a 5.5 and a 1.5 year old and we like to spend as much time as we can get with them when we are not working. Summers are the best because we spend a lot of time outdoors hitting the trails and pools.

Which profession would you choose if you were not a scientist?

I have thought about this question a lot and my answer hasn’t changed in a while. I would like to host and produce a science radio show, similar to Radiolab, that mixes physical and social sciences with personal stories. The one thing I would do differently would be to focus on geographies, cultures, and topics relevant to the developing world.

Can you share one piece of career-related advice or wisdom with other early career scientists?

The one thing I would tell early-career scientists is that don’t take any advice (including this one!) too seriously. Listen, but forge your own path. Don’t be afraid to make mistakes and don’t hold any regrets.

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Emerging Investigator Series – Karen Dannemiller

Karen C. Dannemiller, PhD is an Assistant Professor at Ohio State University with a joint appointment in Civil, Environmental, and Geodetic Engineering and Environmental Health Sciences. She also has a courtesy appointment in Microbiology. At Ohio State, she leads the Indoor Environmental Quality (IEQ) (https://ieq.engineering.osu.edu/) group and studies the indoor microbiome and indoor chemical exposures. In 2017, she was awarded the Denman Distinguished Research Mentor Award.

Prior to her current position, Dr. Dannemiller graduated with honors in Chemical and Biochemical Engineering from Brown University and earned her MS, MPhil, and PhD at Yale University in Chemical and Environmental Engineering. During this time, she completed an internship at the California Department of Public Health in the Indoor Air Quality Program. She was also a Microbiology of the Built Environment Postdoctoral Associate at Yale University

Read Karen Dannemiller’s Emerging Investigator article “Degradation of phthalate esters in floor dust at elevated relative humidity” and find out more about her in the interview below:

Your recent Emerging Investigator Series paper focuses on the degradation of phthalate esters in floor dust at elevated relative humidity. How has your research evolved from your first article to this most recent article?

This paper has really allowed my work to come full circle.  My first research paper was on formaldehyde in the indoor environment, which was based on my work in the chemical engineering department at Brown University as an undergraduate.  During my PhD, I began to focus more on microbial exposures in the indoor environment.  This Emerging Investigator Series paper is so exciting because it combines my interest in both indoor chemistry and indoor microbiology by examining the interactions between these two systems.

What aspect of your work are you most excited about at the moment?

I direct the Indoor Environmental Quality Laboratory at Ohio State University, and I am excited about all the applications that we are discovering to which we can apply our research. It is so critical to understand the chemical and microbial processes occurring in the indoor environment, and this has important implications in many different systems.  These processes can be particularly important in influencing exposures of vulnerable populations, such as asthmatic children.  We also need a thorough understanding of chemical and microbial interactions in specialized, sensitive systems such as on the International Space Station.  I am most excited to have received grants from NIH, NASA, the Alfred P. Sloan Foundation, and other organizations to study these interactions.

In your opinion, what are the most important questions to be asked/answered in this field of research?

Right now, very little is known about the interactions between chemicals and microbes in the indoor environment.  There are a plethora of questions that need to be asked to gain even a basic understanding of what is happening around us on a daily basis.  These may have important implications for our health.

What do you find most challenging about your research?

One of the most challenging but also exciting aspects of my research are the unexpected surprises inherent in any scientific dataset, but especially rich microbial datasets.  Often, future grant proposals can result from novel associations discovered during data analysis.

In which upcoming conferences or events may our readers meet you?

The next conference I will attend will be AEESP in Tempe, AZ, May 14-16, 2019.  I am very excited to be giving the plenary talk on Thursday morning.

How do you spend your spare time?

I love spending time with my family.

Which profession would you choose if you were not a scientist?

If I were not a research scientist, I would be an environmental public health practitioner.  They apply scientific principles to help people reduce their harmful exposures.  I appreciate the hard, challenging work that they do everyday, especially in fields like mold remediation.

Can you share one piece of career-related advice or wisdom with other early career scientists?

I have been very lucky and very thankful to have some outstanding mentors throughout my career.  I would highly recommend that early career scientists find mentors to help them navigate different obstacles they may encounter.  Mentors are a great source of advice and inspiration.  They can also help you identify exciting opportunities

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