Oceanography The Official Magazine of
The Oceanography Society
Volume 30 Issue 04

View Issue TOC
Volume 30, No. 4
Pages 48 - 59

OpenAccess

Creating the Art of Deep-Sea Experimental Chemistry with MBARI ROVs

By Peter G. Brewer , Edward T. Peltzer, Peter M. Walz, and William J. Kirkwood 
Jump to
Article Abstract Citation References Copyright & Usage
Article Abstract

Ocean chemistry has been almost exclusively based upon retrieving samples from the ocean for laboratory or shipboard analysis, or deploying sensors to recover natural signals. The ability to execute complex experiments in the deep ocean akin to the manipulations carried out in laboratories has largely been absent. In this paper, we review the progress made in manipulating and sensing complex gases, liquids, and solids in real time in the deep sea to advance understanding of natural processes. These experiments were made possible by access to the remarkable capabilities of Monterey Bay Aquarium Research Institute’s (MBARI’s) remotely operated vehicle and the skills of the operational teams. Here, we report on advances made in methane hydrate research and deep-ocean Raman spectroscopy, and on proposals for fossil fuel CO2 sequestration and on controlled ocean acidification studies. The skills necessary to advance this work have been made possible only by the joint efforts of engineers and scientists as envisaged by MBARI’s founder. We note with some concern that in reporting progress here there were few antecedents to draw upon, so that the citations listed have a distinctly unbalanced look. Nonetheless, the impacts of the institute’s work have been far-reaching.

Citation

Brewer, P.G., E.T. Peltzer, P.M. Walz, and W.J. Kirkwood. 2017. Creating the art of deep-sea experimental chemistry with MBARI ROVs. Oceanography 30(4):48–59, https://doi.org/10.5670/oceanog.2017.423.

References

Barry, J.P., B.A. Seibel, J.C. Drazen, M.N. Tamburri, K.R. Buck, C. Lovera, L. Kuhnz, E.T. Peltzer, K. Osborn, P.J. Whaling, and others. 2003. Deep-sea field experiments on the biological impacts of direct deep-sea CO2 injection. In Proceedings of the Second Annual Conference on Carbon Sequestration. US Department of Energy.

Barry, J.P., K.R. Buck, C.F. Lovera, L. Kuhnz, P.J. Whaling, E.T. Peltzer, P. Walz, and P.G. Brewer. 2004. Effects of direct ocean CO2 injection on deep-sea meiofauna. Journal of Oceanography 60:759–766, https://doi.org/​10.1007/s10872-004-5768-8.

Barry, J.P., C. Lovera, K.R. Buck, E.T. Peltzer, J.R. Taylor, P.M. Walz, P.J. Whaling, and P.G. Brewer. 2014. Use of a free ocean CO2 enrichment (FOCE) system to evaluate the effects of ocean acidification on the foraging behavior of a deep-sea urchin. Environmental Science & Technology 48(16):9,890–9,897, https://doi.org/​10.1021/es501603r.

Brewer, P.G. 1978. Direct observation of the oceanic CO2 increase. Geophysical Research Letters 5:997–1,000, https://doi.org/10.1029/GL005i012p00997.

Brewer, P.G. 1997. Ocean chemistry of the fossil fuel CO2 signal: The haline signature of “business as usual.” Geophysical Research Letters 24:1,367–1,369, https://doi.org/​10.1029/​97GL01179.

Brewer, P.G. 2000. Contemplating action: Storing carbon dioxide in the ocean. Oceanography 13(2):84–92, https://doi.org/​10.5670/oceanog.2000.38.

Brewer, P.G. 2004. Direct injection of CO2 in the ocean. Pp. 469–478 in Toward CO2 Stabilization: Issues, Strategies, and Consequences. C. Field and M.R. Raupach, eds, Island Press.

Brewer, P.G. 2007. Evaluating a technological fix for climate. Proceedings of the National Academy of Sciences of the United States of America 104:9,915–9,916, https://doi.org/10.1073/pnas.0703892104.

Brewer, P.G., B. Chen, R. Warzinski, A. Baggeroer, E.T. Peltzer, R.M. Dunk, and P. Walz. 2006. Three-dimensional acoustic monitoring and modeling of a deep-sea CO2 droplet cloud. Geophysical Research Letters 33, L23607, https://doi.org/​10.1029/2006GL027181 10.1029/2006GL027181.

Brewer, P.G., G. Friederich, E.T. Peltzer, and F.M. Orr Jr. 1999. Direct experiments on the ocean disposal of fossil fuel CO2. Science 284:943–945, https://doi.org/​10.1126/​science.284.5416.943.

Brewer, P.G., A.F. Hofmann, E.T. Peltzer, and W. Ussler. 2014a. Evaluating microbial chemical choices: The ocean chemistry basis for the competition between use of O2 or NO3 as an electron acceptor. Deep Sea Research Part I 87:35–42, https://doi.org/​10.1016/j.dsr.2014.02.002.

Brewer, P.G., and W.J. Kirkwood. 2013. Raman spectroscopy for subsea applications. Pp. 409–433 in Subsea Optics and Imaging. J. Watson and O. Zielinski, eds, Woodhead Publishing.

Brewer, P.G., G. Malby, J.D. Pasteris, S.N. White, E.T. Peltzer, B. Wopenka, J. Freeman, and M.O. Brown. 2004. Development of a laser Raman spectrometer for deep-ocean science. Deep Sea Research Part I 51:739–753, https://doi.org/​10.1016/​j.dsr.2003.11.005.

Brewer, P.G., F.M. Orr Jr., G. Friederich, K.A. Kvenvolden, and D.L. Orange. 1998. Gas hydrate formation in the deep sea: In situ experiments with controlled release of methane, natural gas and carbon dioxide. Energy & Fuels 12:183–188, https://doi.org/10.1021/ef970172q.

Brewer, P.G., and E.T. Peltzer. 2016. Ocean chemistry, ocean warming, and emerging hypoxia. Journal of Geophysical Research 121:3,659–3,667, https://doi.org/​10.1002/​2016JC011651.

Brewer, P.G., and E.T. Peltzer. 2017. Depth perception: The need to report ocean biogeochemical rates as functions of temperature, not depth. Philosophical Transactions of the Royal Society A, https://doi.org/​10.1098/rsta.2016.0319.

Brewer, P.G., E.T. Peltzer, G. Friederich, and G. Rehder. 2002. Experimental determination of the fate of rising CO2 droplets in sea water. Environmental Science & Technology 36:5,441–5,446, https://doi.org/​10.1021/​es025909r.

Brewer, P.G., E.T. Peltzer, P. Walz, I. Aya, K. Yamane, R. Kojima, Y. Nakajima, N. Nakayama, P. Haugan, and T. Johannessen. 2005. Deep ocean experiments with fossil fuel carbon dioxide: Creation and sensing of a controlled plume at 4 km depth. Journal of Marine Research 63:9–33, https://doi.org/​10.1357/​0022240053693860.

Brewer, P.G., E.T. Peltzer, P.M. Walz, E.K. Coward, L.A. Stern, S.H. Kirby, and J. Pinkston. 2014b. Deep-sea field test of the CH4 hydrate to CO2 hydrate spontaneous conversion hypothesis. Energy & Fuels 28(11):7,061–7,069, https://doi.org/10.1021/ef501430h.

Brewer, P.G., E.T. Peltzer, P.M. Walz, and M. Wojciechowicz. 2017. The speciation of water in sea water and in gelatinous marine animals. Marine Chemistry 195:94–104, https://doi.org/10.1016/​j.marchem.​2017.​05.002.

Burdige, D.J. 2007. Preservation of organic matter in marine sediments: Controls, mechanisms, and an imbalance in sediment organic carbon budgets? Chemical Reviews 107:467–485, https://doi.org/​10.1021/cr050347q.

Caldeira, K., M. Akai, P. Brewer, B. Chen, P. Haugan, T. Iwama, P. Johnston, H. Kheshgi, Q. Li, T. Ohsumi, and others. 2005. Ocean storage. Pp. 277–317 in Carbon Dioxide Capture and Storage: A Special Report of IPCC Working Group III. B. Metz and O. Davidson, eds, Cambridge University Press, Cambridge, UK.

Cicerone, R., J. Orr, P.G. Brewer, P. Haugan, L. Merlivat, T. Ohsumi, S. Pantoja, and H.O. Poertner. 2004. The ocean in a high CO2 world. Eos, Transactions American Geophysical Union 85:351–353, https://doi.org/​10.1029/2004EO370007.

Dunk, R.M., E.T. Peltzer, P. Walz, and P.G. Brewer. 2005. Seeing a deep ocean CO2 enrichment experiment in a new light: Laser Raman detection of dissolved CO2 in seawater. Environmental Science & Technology 39:9,630–9,636, https://doi.org/​10.1021/es0511725.

Gattuso, J.-P., and L. Hansson. 2011. Ocean Acidification. Oxford University Press, 326 pp.

Hanisch, C. 1998. The pros and cons of carbon dioxide dumping. Environmental Science & Technology 32:20A–24A, https://doi.org/10.1021/es983310e.

Holder, G.D., A.V. Cugini, and R.P. Warzinski. 1995. Modeling clathrate hydrate formation during carbon dioxide injection into the ocean. Environmental Science & Technology 29:276–278, https://doi.org/​10.1021/es00001a037.

Kirkwood, W.J., P.M. Walz, E.T. Peltzer, J.P. Barry, R.A. Herlien, K.L. Headley, C. Kecy, G.I. Matsumoto, T. Maughan, T.C. O’Reilly, and others. 2014. Design, construction, operation and performance of a deep-sea free ocean CO2 enrichment (FOCE) experimental system. Deep Sea Research Part I 97:1–9, https://doi.org/10.1016/​j.dsr.2014.11.005.

Kleinberg, R.L. 1996. Well logging. Pp. 4,960–4,969 in Encyclopedia of Nuclear Magnetic Resonance, vol. 8. D.M. Grant and R.K. Harris, eds, Wiley, Chichester.

Kleinberg, R.L., and P.G. Brewer. 2001. Probing gas hydrate deposits. American Scientist 89:244–251.

Kleinberg, R.L., P.G. Brewer, G. Malby, E.T. Peltzer, G. Friederich, J. Yesinowski, and C. Flaum. 2003. Seafloor nuclear magnetic resonance assay of methane hydrate in sediment and rock. Journal of Geophysical Research 108(B3), 2137, https://doi.org/​10.1029/​2001JB000919.

Lee, H., S. Yongwon, Y.-T. Sea, I.L. Moudrakovski, and J.A. Ripmeester. 2003. Recovering methane from solid methane hydrate with carbon dioxide. Angewandte Chemie 115:5,202–5,205, https://doi.org/​10.1002/anie.200351489.

Marchetti, C. 1977. On geoengineering and the CO2 problem. Climatic Change 1:59–68, https://doi.org/​10.1007/BF00162777.

NRC (National Research Council). 2004. Charting the Future of Methane Hydrate Research in the United States. The National Academies Press, Washington, DC, 192 pp.

Ota, M., T. Saito, T. Aida, M. Watanabe, Y. Sato, R.L. Smith Jr., and H. Inomata. 2007. Macro and microscopic CH4−CO2 replacement in CH4 hydrate under pressurized CO2. AIChE Journal 53(10):2,715−2,721, https://doi.org/​10.1002/aic.11294.

Pasteris, J.D., B. Wopenka, J.J. Freeman, P.G. Brewer, S.N. White, E.T. Peltzer, and G. Malby. 2004. Spectroscopic successes and challenges: Raman spectroscopy at 3.6 km depth in the ocean. Applied Spectroscopy 58(7):195A–208A.

Paull, C., and W. Ussler. 2001. History and significance of gas sampling during DSDP and ODP drilling associated with gas hydrates. Pp. 53–65 in Natural Gas Hydrates: Occurrence, Distribution, and Detection. C.K. Paull and W.P. Dillon, eds, American Geophysical Union, Washington, DC, https://doi.org/​10.1029/GM124p0053.

Park, Y., D.Y. Kim, J.W. Lee, D.G. Huh, K.P. Park, J. Lee, and H. Lee. 2006. Sequestering carbon dioxide into complex structures of naturally occurring gas hydrates. Proceedings of the National Academy of Sciences of the United States of America 103(34):12,690−12,694, https://doi.org/​10.1073/pnas.0602251103.

PCAST (President’s Council of Advisors on Science and Technology). 1997. Federal Energy Research and Development Agenda for the Challenges of the Twenty-First Century. US Department of Energy, Washington, DC.

Peltzer, E.T., X. Zhang, P.M. Walz, M. Luna, and P.G. Brewer. 2016. In situ Raman measurement of HS and H2S in sediment pore waters and use of the HS:H2S ratio as an indicator of pore water pH. Marine Chemistry 184:32–42, https://doi.org/​10.1016/j.marchem.2016.05.006.

Raman, C.V. 1930. The molecular scattering of light. Nobel Lecture, December 11, 1930, https://www.nobelprize.org/nobel_prizes/physics/laureates/1930/raman-lecture.pdf.

Reeburgh, W.S. 2007. Oceanic methane biogeochemistry. Chemical Reviews 107:486–513, https://doi.org/​​10.1021/cr050362v.

Rehder, G., P.G. Brewer, E.T. Peltzer, and G. Friederich. 2002. Enhanced lifetime of methane bubble streams within the deep ocean. Geophysical Research Letters 29(15), https://doi.org/​10.1029/​2001GL013966.

Rehder, G., S.H. Kirby, W.B. Durham, L.A. Stern, E.T. Peltzer, J. Pinkston, and P.G. Brewer. 2004. Dissolution rates of pure methane hydrate and carbon dioxide hydrate in under-saturated seawater at 1000-m depth. Geochimica et Cosmochima Acta 68(2):285–292, https://doi.org/10.1016/​j.gca.2003.07.001.

Rubey, W.W. 1951. Geologic history of seawater: An attempt to state the problem. Bulletin of the Geological Society of America 62:1,111–1,148, https://doi.org/​10.1130/​0016-​7606(1951)62​​[1111:​GHOSW]​2.0.CO;2.

Sillén, L.G. 1961. The physical chemistry of sea water. Pp. 549–581 in Oceanography. M. Sears, ed., American Association for the Advancement of Science, Washington, DC.

Sloan, E.D. 1997. Clathrate Hydrates of Natural Gases. Marcel Dekker, Inc., New York.

Sonnerup, R.E., S. Mecking, and J.L. Bullister. 2013. Transit time distributions and oxygen utilization rates in the Northeast Pacific Ocean from chlorofluorocarbons and sulfur hexafluoride. Deep Sea Research Part I 72:61–71, https://doi.org/10.1016/​j.dsr.2012.10.013.

Stanley, R.H.R., S.C. Doney, W.J. Jenkins, and D.E. Lott. 2012. Apparent oxygen utilization rates calculated from tritium and helium-3 profiles at the Bermuda Atlantic Time-series Study site. Biogeosciences 9:1,969–1,983, https://doi.org/​10.5194/bg-9-1969-2012.

Sum, A.K., R.C. Burruss, and E.D. Sloan Jr. 1997. Measurement of clathrate hydrates via Raman spectroscopy. The Journal of Physical Chemistry 101:7,371–7,377, https://doi.org/10.1021/jp970768e.

Tsouris, C., P.G. Brewer, E. Peltzer, P. Walz, D. Riestenberg, L. Liang, and O.R. West. 2004. Hydrate composite particles for ocean carbon sequestration: Field verification. Environmental Science & Technology 38:2,470–2,475, https://doi.org/10.1021/es034990a.

Tsouris, C., P. Szymcek, P. Taboada-Serrano, S.D. McCallum. P.G. Brewer, E.T. Peltzer, P. Walz, E. Adams, A. Chow, W.K. Johnson, and J. Summers. 2007. Scaled-up injection of CO2-hydrate composite particles. Energy & Fuels 21:3,300–3,309, https://doi.org/10.1021/ef070197h.

Zhang, X., P. Walz, W.J. Kirkwood, K.C. Hester, W. Ussler, E.T. Peltzer, and P.G. Brewer. 2010. Development and deployment of a deep-sea Raman probe for measurement of pore water geochemistry. Deep Sea Research Part I 57:297–306, https://doi.org/10.1016/j.dsr.2009.11.004.

Zhang, X., K.C. Hester, W. Ussler, P.M. Walz, E.T. Peltzer, and P.G. Brewer. 2011. In situ Raman-based measurements of high dissolved methane concentrations in hydrate-rich ocean sediments. Geophysical Research Letters 38, L08605, https://doi.org/10.1029/2011GL047141.

Copyright & Usage

This is an open access article made available under the terms of the Creative Commons Attribution 4.0 International License (https://creativecommons.org/licenses/by/4.0/), which permits use, sharing, adaptation, distribution, and reproduction in any medium or format as long as users cite the materials appropriately, provide a link to the Creative Commons license, and indicate the changes that were made to the original content. Images, animations, videos, or other third-party material used in articles are included in the Creative Commons license unless indicated otherwise in a credit line to the material. If the material is not included in the article’s Creative Commons license, users will need to obtain permission directly from the license holder to reproduce the material.