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The Collaborative on Oceanography and Chemical Analysis (COCA) and Suggestions for Future Instrumental Analysis Methods in Chemical Oceanography

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The Collaborative on Oceanography and Chemical Analysis (COCA) and Suggestions for Future Instrumental Analysis Methods in Chemical Oceanography The Collaborative on Oceanography and Chemical Analysis (COCA) and suggestions for future instrumental analysis methods in chemical oceanography COCA Working Group*1 *Corresponding author Chris Measures, Department of Oceanography, University of Hawaii, 1000 Pope Road, Honolulu, HI, 96822, USA. Tel +1 808-956-8693 Email: [email protected] 1 The members of the COCA Working group are listed in Appendix I Submitted to a special issue of Marine Chemistry June, 2014. Abstract The ability to make measurements accurately and precisely is the sine qua non of chemical oceanography. The development of theory and its transformation into modeling is completely dependant on the understanding gained through accurate measurements of oceanic properties. Chemical oceanographers, by making measurements of various chemical elements in ocean water, seek to discover, understand, and quantify ocean processes and use them in conjunction with other branches of oceanography to understand how the oceans interact with Earth system processes. We use this information to understand how the planetary biogeochemical systems affect and interact with the climate and use the chemical record in the sediments to understand how these systems operated in the past. With this knowledge we can build accurate models to predict responses to future climate forcing events. The primary inputs to chemical oceanography are dominantly provided by applied analytical chemistry. The construction of large networked observing systems and the development of a variety of autonomous vehicles have provided an unprecedented opportunity to study the ocean at spatial and temporal scales that have not been previously available to the ocean research community. However, as a result of power availability, mass and size constraints, and the limited ability to service instruments on these platforms, there are only a few parameters of interest to chemical oceanographers that can take advantage of this expensive infrastructure. There is thus an urgent need to develop new methodologies in oceanography that can meet these constraints on the development and deployment of new sensors, and a need to catalyze interactions among chemical oceanographers, analytical chemists, and ocean engineers to bring new technologies into use for ocean sensors. Analytical chemistry at this time is one of the most rapidly evolving areas; as a result it is difficult if not impossible for chemical oceanographers to remain cognizant of fundamental improvements in the field of analytical chemistry that could be profitably adapted for use in oceanography. This need to bridge the gap between chemical oceanographers and analytical chemists has been recognized for a long time (Goldberg, 1988) and past suggestions to improve the measurement of carbon system parameters (among others), Walt and Urban, 1995; NRC, 1993, have produced tangible results. However, in rapidly changing fields the connection between the fields needs to be reinforced at regular intervals or, preferably, on a semi-continuous basis. This manuscript summarises a meeting that was held at the Department of Oceanography, University of Hawaii, March 26-29, 2013. The purpose of the meeting was to bring together chemical oceanographers and analytical chemists to explore new developments in analytical chemistry that might be developed for use in oceanography. This manuscript has been condensed from the text provided by the attendees who are listed in Appendix 1. It is important to realize that this summary reflects all of those ideas, it does not therefore represent a consensus view. The plenary talks and the full text of the working group reports, and their members, are available on line at the workshop web site: http://www.soest.hawaii.edu/oceanography/faculty/chrism/COCA/Home.html 1. The rationale driving oceanographic chemical analyses. Chemical Oceanography aims to quantitatively account for distributions of elements and molecules in the ocean by determining their external sources and sinks, their internal fluxes, and their internal chemical and biological interactions. By making measurements of chemical elements, molecules, and stable and radioactive isotopes in the ocean, chemical oceanographers seek to discover, understand, and quantify ocean processes and use them in conjunction with other branches of oceanography to understand the role of the ocean in the Earth System. We use this information to understand how planetary biogeochemical systems affect and respond to climate. Some of these properties actively affect the global climate system (e.g. carbon and its related properties such as nutrients), while others serve as paleoclimate proxies that help assess processes that have caused past climate changes. This effort must take into account the physical circulation of the ocean as a major factor impacting chemical distributions, as ocean currents and mixing moves water from reactive boundaries (air-sea, sediment-water, light-dark, submarine volcanic centers) into the interior. Dissolved constituents interact with the sinking particulate flux to move constituents downwards and remove many substances into sediments. This knowledge can be used to understand chemical records contained in oceanic sediments that reflect past changes in ocean circulation and processes and also to construct mathematical models that can be used to predict oceanic responses to evolving climate forcing. To achieve this knowledge, oceanographers need to develop extensive data- bases for a variety of critical chemical species that have been found to trace important oceanographic processes. The types of data needed vary considerably ranging from high-resolution temporal and spatial sampling in regions with strong chemical and biological gradients and rapid water flows to relatively low sampling rates in more quiescent open ocean regions with weak gradients. In addition temporal records are needed from fixed sampling systems (moorings) as well as from autonomous programmed (sea gliders) or free drifting (floats) vehicles that can sample unattended for long time periods as well as operate in hostile environments and inaccessible regions. Chemical concentrations in the ocean range from ~0.6 M for the major ions of NaCl down to femtomolar or lower for some short lived radioactive species. Every naturally occurring element is present in seawater, as are most of those produced by radioactive decay. These materials can occur in multiple oxidation states and can be associated with a variety of complexing ligands both organic and inorganic. Thus analytical methodology is challenged not only by exceedingly low abundances, but also by the presence of virtually every other element including neighbouring periodic table group members with similar reactivities. In addition many of the analytes of interest that occur at the lowest concentrations in the ocean are commonly used in manufactured materials or mobilised in large amounts in human activities so that contamination of natural concentrations by anthropogenic sources including those associated with water samplers and sampling platforms is a major obstacle. Thus oceanography requires a variety of analytical methodological approaches to making these measurements and depending on the problem being approached these methodologies have a variety of constraints. For example large- scale expedition style ship-based sampling where water sampling from the surface to the bottom of the ocean is repeated at intervals of 30-60 km needs relatively rapid shipboard analysis (8-10 samples/hr), but has little constraints in terms of power requirements. For sensors that can be attached to the packages deployed from ships sampling rates of several Hz are needed and the detection system must be able to function at pressures up to 600 atmospheres. For autonomous sampling devices, such as sea gliders and Argo floats, that have relatively slow translation speeds the main constraint is the availability of electrical power, but the stability of the instrument and the ability to calibrate the signals produced becomes crucial as deployment times increase. Similarly the volume of reagent use and its chemical stability under oceanic conditions also become very important for devices that are free floating. Devices on moorings deployed in coastal regions with high levels of synoptic variability and strong spatial gradients in water column and sediment properties require high frequency or continuous sampling to resolve processes. Similar types of moorings deployed in remote or hostile marine environments may not require such high frequency sampling but need to be calibrated in situ and maintenance free for periods of a year or more Currently many properties of interest to oceanographers are determined on samples returned to shore-based laboratories. This can be either because of lack of methodology compatible with use at sea or because shipboard space is limited. In many cases because of low analyte concentrations these properties require large volumes of water the shipping of which is both expensive and can present severe logistical problems. Thus, there are many needs in oceanography that can benefit from the latest developments in analytical chemistry they can be summarised as desires for: Low power consumption Increased speed of determinations Low detection limits High precision Low maintenance Insensitivity to typical shipboard vibrations and accelerations The ability to be calibrated in situ High specificity for the target analyte 2. Current state of the art Currently
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