Mass Spectrometry Analysis Sheds Light on Mysterious Marine Debris

Recently, the New York Times published a story (1) centered on mysterious blobs found along Placentia Bay, a body of water on the southeast coast of Newfoundland, Canada, and the efforts of chemist Christopher Kozak, part of Memorial University/Newfoundland and Labrador University’s Green Chemistry and Catalysis Group, to identify its makeup and source (2). LCGC International spoke with Kozak about this research and the techniques he and his team used in this research.

How did you first become aware of the so called “blobs”?

I had read about them in the local news in early October and thought to myself, “Why hasn’t anyone reached out to a chemist about this?” A colleague in our Earth Sciences department called me to say she had some samples of the blob and was planning on looking into them, but quickly identified they weren’t natural, and therefore outside her area of expertise.

What motivated you to consider trying to identify the makeup of the substance of these “blobs”?

I like a good puzzle, and structure elucidation was one of my favorite aspects of chemistry when I was a student. We had recently acquired a beautiful suite of advanced instrumentation, including chromatography and mass spectrometry systems, nuclear magnetic resonance, materials/polymer characterization equipment, and elemental analysis. This was a great opportunity to put our new instruments to the test.

Your selected mass spectrometry (MS) for your analysis. Why did you choose that analytical approach?

I have long been a fan of MS for characterizing small molecules and polymers, but also for structure elucidation of our transition metal complexes, and even for tracking reaction intermediates in catalytic reactions. We have at our disposal several gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS) instruments including a triple quadrupole mass spectrometer (TQMS), a time-of-flight mass spectrometer (TOF), two quadrupole time-of-flight (Q-TOF) spectrometry systems, plus a matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometer. Our mass spectrometry facility is outstanding. Here we used MALDI-TOF MS because of our success with that technique for polymer characterization as part of our research program. Sample solubility was extremely low to negligible, so solution injection techniques may have been problematic. With MALDI, it was less of an issue. We also use excellent software, Polymerix (Sierra Analytics), for deconvoluting complex spectra and that helped us identify different fragments that helped us in identifying the nature of the “blobs.”

Did you go into your investigations with any preconceived notions of what the substance might be?

Once I knew it was synthetic (it had a volatile organic compounds [VOC] odor to it and didn’t suggest biological matter), I thought about what sorts of polymers/adhesives would be found around the area. Newfoundland has large fishing, mining and offshore oil industries, so those could have been the sources. I know polyurethane is used as insulation in the holds of fishing boats, so that was my first notion. We also had infrared spectroscopy confirm the presence of O-H, C-H and carbonyl bands, consistent with a urethane. Elemental analysis for carbon (C), hydrogen (H), nitrogen (N) and sulfur (S) eliminated that as our results came back showing 0% N and 0% S. We know oxygen (O) was present from the infrared (IR) spectroscopy and thermogravimetric analysis (TGA) [CH1] [CK2] showed 18% water content. Eliminating possibilities helped us narrow down our investigation.

What are the key findings of your investigation?

The key discovery was that it was a synthetic polymer mixture containing C, H and O, with ester groups and unsaturated sites. Using nuclear magnetic resonance (1H NMR) spectroscopy, we observed no aromatic groups, only aliphatic protons of alkane and alkene sites, as well as acyl groups. MS using MALDI-TOF confirmed vinyl acetate, but also showing isoprene, butadiene and other fragments from a synthetic polymeric hydrocarbon, possibly polyisoprene. The “blobs” appear to be a mixture of polymers. We suspected it could be polyethylene vinyl acetate (PEVA), which is elastomeric and rubber-like, but PEVA is noticeably more soluble in solvents such as toluene, chloroform, and hexane.

Were any unexpected results that required you to change anything about your experimentation?

Not really. With my graduate students we proposed a list of experiments and analyses to perform and followed through with them, seeing how each technique produced another piece of the puzzle.

What challenges did you encounter in your research?

In the case of the “blobs,” their poor solubility did slow us down and limited what we could do with them. Once we got them into chloroform following sonication, we now had the potential for NMR and spotting samples for MALDI-TOF more easily.

What practical applications or future research could come from your work?

Well, the analysis of the “blobs” was a side quest for us. We don’t normally seek out curious elastomeric masses on Canadian beaches, but we are synthetic chemists working on making new polymers through controlled, metal-catalyzed reactions. This was a good lesson for our graduate students in the different characterization methods at their disposal.

What are your currently working on in your laboratory?

Work in our laboratory focuses on making transition and main group metal complexes that catalyze polymerization and copolymerization of monomers such as epoxides, anhydrides, CO2 and biomass-derived feedstocks.

Doing a quick internet search, I found that things like this happen more often than one might suppose. For instance, there was a 2022 story covered by LiveScience where the mysterious entity in question turned out to be a living thing (3). Did you do any research on similar instances of unidentified substances, and did you find anything particularly interesting that influenced your investigation?

I was familiar with a case a few years ago in Newfoundland where a large mass of material washed up on a beach, which turned out to be biological, coming from a decaying whale carcass. On the other hand, I had found many stories of blob-like masses washing ashore that were the result of oil-spill clean-up efforts. It was the oil-spill dispersants that I thought might be a source for the blobs I studied, or something else related to the offshore oil industry.

Can you please summarize the feedback that you have received from others regarding this work?

I have heard from several of my colleagues and my network of academic chemists congratulating me on solving this puzzle, as well as from people in the community thanking me for clearing this up for them. I have also heard from people suggesting possible sources, or sharing their own experiences of finding odd, shapeless masses washed ashore in places around the world.

Are there any next steps regarding this research?

I think I have done as much as I can in terms of analysis. My colleague in Earth Sciences has started investigating the plants and algae trapped in the matrix of the blobs. This might inform us of where this stuff entered the ocean. It was clearly liquid at some point judging from the way pebbles and sea weeds became entrapped within it. Where these plants might be those typically found closer to shore, it might suggest that the origin of the blobs was a spill closer to shore within Placentia Bay rather than further afield.

Christopher Kozak is a professor of chemistry at Memorial University of Newfoundland in St. John’s, Canada. He obtained his B.Sc. in Biological Chemistry from McMaster University in Hamilton, Ontario in 1997. He then moved to The University of British Columbia in Vancouver to obtain his PhD. In 2002 he moved to the UK to perform postdoctoral research at the University of York, followed by a Natural Sciences and Engineering Research Council (NSERC) postdoctoral fellowship at The University of Oxford. In 2004, he moved back to Canada and took up a position as an Assistant Professor at Concordia University in Montreal, Quebec. In 2005 he moved to his current position at Memorial University. His research focuses on earth-abundant transition metal-catalyzed polymerization of renewable feedstocks including CO2, cyclic esters, anhydrides and epoxides. In 2020 he and a team of colleagues received funding from the Canada Foundation for Innovation and the provinces of Newfoundland and Labrador and Nova Scotia to create the Atlantic Canada Environmental and Sustainable Chemistry and Engineering Centre. This funding allowed for a massive investment in the core research instrumentation in the region, transforming the analytical capabilities at Memorial University.

References

1. Mystery “Blobs” Washing Up in Newfoundland May Have Been Identified Through MS. ChromatographyOnline website. https://www.chromatographyonline.com/view/mystery-blobs-washing-up-in-newfoundland-may-have-been-identified-through-ms(accessed 2024-11-22).

2. Chemist Identifies Mystery ‘Blobs’ Washing Up in Newfoundland. New York Times website. https://www.nytimes.com/2024/11/14/world/canada/blobs-canada-newfoundland.html?unlocked_article_code=1.aU4.stl6.yUDAJ2sE3xt2&smid=url-share (accessed 2024-11-22).

3. Baker, H. Mysterious 'Blue Goo' at the Bottom of the Sea Stumps Scientists. LiveScience webpage. https://www.livescience.com/mysterious-blue-goo-deep-sea (accessed 2024-11-20)