Laboratory evaluation of laser-induced breakdown spectroscopy (LIBS) as a new in situ chemical sensing technique for the deep ocean

Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution September 2007Present-day expeditionary oceanography is beginning to shift from a focus on short- term ship and submersible deployments to an ocean observatory mode where long- term temporally-focused studies are feasible. As a result, a critical need for in situ chemical sensors is evolving. New sensors take a significant amount of time to develop; thus, the evaluation of techniques in the laboratory for use in the ocean environment is becoming increasingly important. Laser-induced breakdown spectroscopy (LIBS) possesses many of the characteristics required for such in situ chemical sensing, and is a promising technique for field measurements in extreme environments. Although many LIBS researchers have focused their work on liquid jets or surfaces, little at- tention has been paid to bulk liquid analysis, and especially to the effect of oceanic pressures on LIBS signals. In this work, laboratory experiments validate the LIBS technique in a simulated deep ocean environment to pressures up to 2.76 × 107 Pa. A key focus of this work is the validation that select elements important for understand- ing hydrothermal vent fluid chemistry (Na, Ca, Mn, Mg, K, and Li) are detectable using LIBS. A data processing scheme that accurately deals with the extreme nature of laser-induced plasma formation was developed that allows for statistically accu- rate comparisons of spectra. The use of both single and double pulse LIBS for high pressure bulk aqueous solutions is explored and the system parameters needed for the detection of the key analytes are optimized. Using both single and double pulse LIBS, the limits of detection were found to be higher than expected as a result of the spectrometer used in this experimentation. However, the results of this validation show that LIBS possesses the characteristics to be a viable chemical sensing method for in situ analyte detection in high pressure environments like the deep ocean.National Science Foundation for support of this research under grants OCE0352278 and OCE0352242. Additional support was received from WHOI’s Deep Ocean Exploration Institute who awarded this research with two grants. The WHOI Ocean Ventures Fund and the Department of Defens

Laser induced breakdown spectroscopy for heavy metal detection in a sand matrix

© The Author(s), 2016. This is the author's version of the work and is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Spectrochimica Acta Part B: Atomic Spectroscopy 125 (2016):177-183, doi:10.1016/j.sab.2016.10.001.Sediments in many locations, including harbors and coastal areas, can become contaminated and polluted, for example, from anthropogenic inputs, shipping, human activities, and poor waste management. Sampling followed by laboratory analysis has been the traditional methodology for such analysis. In order to develop rapid methodologies for eld analysis of sediment samples, especially for metals analyses, we look to Laser Induced Breakdown Spectroscopy as an option. Here through laboratory experiments, we demonstrate that dry sand samples can be rapidly analyzed for the detection of the heavy metals chromium, zinc, lead, and copper. We also demonstrate that cadmium and nickel are detectable in sand matrices at high concentrations.This work is supported by funding from the National Science Foundation (OCE-RIG: 1322704) and the Woods Hole Oceanographic Institution by The Penzance Endowed Fund in Support of Assistant Scientists and The Reuben F. and Elizabeth B. Richards Endowed Fund in Support of Scienti c Sta .2018-10-0

Flow-through quantification of microplastics using impedance spectroscopy

© The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Colson, B. C., & Michel, A. P. M. Flow-through quantification of microplastics using impedance spectroscopy. ACS Sensors, 6(1), (2021): 238–244, doi:10.1021/acssensors.0c02223.Understanding the sources, impacts, and fate of microplastics in the environment is critical for assessing the potential risks of these anthropogenic particles. However, our ability to quantify and identify microplastics in aquatic ecosystems is limited by the lack of rapid techniques that do not require visual sorting or preprocessing. Here, we demonstrate the use of impedance spectroscopy for high-throughput flow-through microplastic quantification, with the goal of rapid measurement of microplastic concentration and size. Impedance spectroscopy characterizes the electrical properties of individual particles directly in the flow of water, allowing for simultaneous sizing and material identification. To demonstrate the technique, spike and recovery experiments were conducted in tap water with 212–1000 μm polyethylene beads in six size ranges and a variety of similarly sized biological materials. Microplastics were reliably detected, sized, and differentiated from biological materials via their electrical properties at an average flow rate of 103 ± 8 mL/min. The recovery rate was ≥90% for microplastics in the 300–1000 μm size range, and the false positive rate for the misidentification of the biological material as plastic was 1%. Impedance spectroscopy allowed for the identification of microplastics directly in water without visual sorting or filtration, demonstrating its use for flow-through sensing.The authors thank the Richard Saltonstall Charitable Foundation and the National Academies Keck Futures Initiative (NAKFI DBS13) for their funding support

Observations of shallow methane bubble emissions from Cascadia Margin

© The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Michel, A. P. M., Preston, V. L., Fauria, K. E., & Nicholson, D. P. Observations of shallow methane bubble emissions from Cascadia Margin. Frontiers in Earth Science, 9, (2021): 613234, https://doi.org/10.3389/feart.2021.613234.Open questions exist about whether methane emitted from active seafloor seeps reaches the surface ocean to be subsequently ventilated to the atmosphere. Water depth variability, coupled with the transient nature of methane bubble plumes, adds complexity to examining these questions. Little data exist which trace methane transport from release at a seep into the water column. Here, we demonstrate a coupled technological approach for examining methane transport, combining multibeam sonar, a field-portable laser-based spectrometer, and the ChemYak, a robotic surface kayak, at two shallow (<75 m depth) seep sites on the Cascadia Margin. We demonstrate the presence of elevated methane (above the methane equilibration concentration with the atmosphere) throughout the water column. We observe areas of elevated dissolved methane at the surface, suggesting that at these shallow seep sites, methane is reaching the air-sea interface and is being emitted to the atmosphere.Funding for VP was provided by an NDSEG Fellowship. Funding for KF was provided by a WHOI Postdoctoral Scholar Fellowship. Ship time on the R/V Falkor was provided by the Schmidt Ocean Institute (FK180824)

Accelerating global ocean observing: monitoring the coastal ocean through broadly accessible, low-cost sensor networks

© The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Wang, Z. A., Michel, A. P. M., & Mooney, T. A. Accelerating global ocean observing: monitoring the coastal ocean through broadly accessible, low-cost sensor networks. Marine Technology Society Journal, 55(3), (2021): 82–83, https://doi.org/10.4031/MTSJ.55.3.52.The global coastal ocean provides food and other critical resources to human societies. Yet this habitat, for which many depend, has experienced severe degradation from human activities. The rates of human-induced changes along the coast demand significantly improved coverage of ocean observations in order to support science-based decision making and policy formation tailored to specific regions. Our proposal envisions developing a global network of low-cost, easily produced and readily deployed oceanographic sensors for use on a wide variety of platforms in the coastal ocean. A substantially large number of these sensors can thus be installed on existing infrastructure, ships of opportunity, and fishing fleets, or even individually along the coast, particularly in vulnerable and disadvantaged regions. This would vastly increase the spatiotemporal resolution of the current data coverage along the coast, allowing greater equitable access. It would also offer significant opportunities for partnership with communities, NGOs, governments, and other stakeholders, as well as a wide range of commercial and industrial sectors to develop and deploy sensors in scalable networks transmitting data in near-real time. Finally, it presents a vastly lowered bar for participation by citizen scientists and other engaged members of the public to address location-specific coastal problems anywhere in the world.National Science Foundation; Project Title “Collaborative Research: IDBR: Type A: A High-resolution bio-sensor to simultaneously measure the behavior, vital rates and environment of key marine organisms”; Award Number 1455593 to ZAW and TAM

Long-path quantum cascade laser–based sensor for methane measurements

Author Posting. © American Meteorological Society, 2016. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Atmospheric and Oceanic Technology 33 (2016): 2373-2384, doi:10.1175/JTECH-D-16-0024.1.A long-path methane (CH4) sensor was developed and field deployed using an 8-μm quantum cascade laser. The high optical power (40 mW) of the laser allowed for path-integrated measurements of ambient CH4 at total pathlengths from 100 to 1200 m with the use of a retroreflector. Wavelength modulation spectroscopy was used to make high-precision measurements of atmospheric pressure–broadened CH4 absorption over these long distances. An in-line reference cell with higher harmonic detection provided metrics of system stability in rapidly changing and harsh environments. The system consumed less than 100 W of power and required no consumables. The measurements intercompared favorably (typically less than 5% difference) with a commercial in situ methane sensor when accounting for the different spatiotemporal scales of the measurements. The sensor was field deployed for 2 weeks at an arctic lake to examine the robustness of the approach in harsh field environments. Short-term precision over a 458-m pathlength was 10 ppbv at 1 Hz, equivalent to a signal from a methane enhancement above background of 5 ppmv in a 1-m length. The sensor performed well in a range of harsh environmental conditions, including snow, rain, wind, and changing temperatures. These field measurements demonstrate the capabilities of the approach for use in detecting large but highly variable emissions in arctic environments.The authors gratefully acknowledge funding for this work by MIRTHE through NSF-ERC Grant EEC-0540832. D. J. Miller acknowledges support by the National Science Foundation Graduate Research Fellowship under Grant DGE-0646086. K. Sun acknowledges support by the NASA Earth and Space Science Fellowship IIP-1263579.2017-05-0

Divergent forms of pyroplastic: lessons learned from the M/V X-Press Pearl ship fire

© The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in James, B., de Vos, A., Aluwihare, L., Youngs, S., Ward, C., Nelson, R., Michel, A., Hahn, M., & Reddy, C. Divergent forms of pyroplastic: lessons learned from the M/V X-Press Pearl ship fire. ACS Environmental Au, 2(5), (2022): 467–479, https://doi.org/10.1021/acsenvironau.2c00020.In late May 2021, the M/V X-Press Pearl container ship caught fire while anchored 18 km off the coast of Colombo, Sri Lanka and spilled upward of 70 billion pieces of plastic or “nurdles” (∼1680 tons), littering the country’s coastline. Exposure to combustion, heat, chemicals, and petroleum products led to an apparent continuum of changes from no obvious effects to pieces consistent with previous reports of melted and burned plastic (pyroplastic) found on beaches. At the middle of this continuum, nurdles were discolored but appeared to retain their prefire morphology, resembling nurdles that had been weathered in the environment. We performed a detailed investigation of the physical and surface properties of discolored nurdles collected on a beach 5 days after the ship caught fire and within 24 h of their arrival onshore. The color was the most striking trait of the plastic: white for nurdles with minimal alteration from the accident, orange for nurdles containing antioxidant degradation products formed by exposure to heat, and gray for partially combusted nurdles. Our color analyses indicate that this fraction of the plastic released from the ship was not a continuum but instead diverged into distinct groups. Fire left the gray nurdles scorched, with entrained particles and pools of melted plastic, and covered in soot, representing partial pyroplastics, a new subtype of pyroplastic. Cross sections showed that the heat- and fire-induced changes were superficial, leaving the surfaces more hydrophilic but the interior relatively untouched. These results provide timely and actionable information to responders to reevaluate cleanup end points, monitor the recurrence of these spilled nurdles, gauge short- and long-term effects of the spilled nurdles to the local ecosystem, and manage the recovery of the spill. These findings underscore partially combusted plastic (pyroplastic) as a type of plastic pollution that has yet to be fully explored despite the frequency at which plastic is burned globally.This work was supported by the Postdoctoral Scholar Program at the Woods Hole Oceanographic Institution (WHOI), with funding provided by the Weston Howland Jr. Postdoctoral Scholarship. Additional support was provided by the WHOI Marine Microplastics Catalyst Program, the WHOI Marine Microplastics Innovation Accelerator Program, the WHOI Investment in Science Fund, the March Marine Initiative (a program of March Limited, Bermuda), The Seaver Institute, Gerstner Philanthropies, the Wallace Research Foundation, the Richard Saltonstall Charitable Foundation, the Harrison Foundation, Hollis and Ermine Lovell Charitable Foundation, and the Richard Grand Foundation. AdV was supported by funding from the Schmidt Foundation

Quantum cascade laser-based reflectance spectroscopy: a robust approach for the classification of plastic type

© The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Michel, A. P. M., Morrison, A. E., Colson, B. C., Pardis, W. A., Moya, X. A., Harb, C. C., & White, H. K. Quantum cascade laser-based reflectance spectroscopy: a robust approach for the classification of plastic type. Optics Express, 28(12), (2020): 17741-17756, doi:10.1364/OE.393231.The identification of plastic type is important for environmental applications ranging from recycling to understanding the fate of plastics in marine, atmospheric, and terrestrial environments. Infrared reflectance spectroscopy is a powerful approach for plastics identification, requiring only optical access to a sample. The use of visible and near-infrared wavelengths for plastics identification are limiting as dark colored plastics absorb at these wavelengths, producing no reflectance spectra. The use of mid-infrared wavelengths instead enables dark plastics to be identified. Here we demonstrate the capability to utilize a pulsed, widely-tunable (5.59 - 7.41 µm) mid-infrared quantum cascade laser, as the source for reflectance spectroscopy, for the rapid and robust identification of plastics. Through the application of linear discriminant analysis to the resulting spectral data set, we demonstrate that we can correctly classify five plastic types: polyethylene terephthalate (PET), high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), and polystyrene (PS), with a 97% accuracy rate.Richard Saltonstall Charitable Foundation; National Academies Keck Futures Initiative (NAKFI DBS13)

Further Sunyaev-Zel'dovich observations of two Planck ERCSC clusters with the Arcminute Microkelvin Imager

We present follow-up observations of two galaxy clusters detected blindly via the Sunyaev-Zel'dovich (SZ) effect and released in the Planck Early Release Compact Source Catalogue. We use the Arcminute Microkelvin Imager, a dual-array 14-18 GHz radio interferometer. After radio source subtraction, we find a SZ decrement of integrated flux density -1.08+/-0.10 mJy toward PLCKESZ G121.11+57.01, and improve the position measurement of the cluster, finding the centre to be RA 12 59 36.4, Dec +60 04 46.8, to an accuracy of 20 arcseconds. The region of PLCKESZ G115.71+17.52 contains strong extended emission, so we are unable to confirm the presence of this cluster via the SZ effect.Comment: 4 tables, 3 figures, revised after referee's comments and resubmitted to MNRA