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Different combinations of parameters must be measured or calculated depending on the biogeochemical processes of interest. The carbonate system can be described by a system of equations such that it can be fully constrained by measuring any two of the four parameters.
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There are four “master” variables for the marine carbonate system that we can measure: partial pressure (or fugacity) of CO 2 ( pCO 2), pH, dissolved inorganic carbon (DIC), and total alkalinity (TA). To observe predicted changes in the ocean carbonate system, we must have an instrumentation network that can capture acidification and its effects at multiple temporal and spatial scales. For example, modeling results predict that some ocean regions will acidify significantly faster than the open ocean, such as upwelling regions like the California Current System, the Arctic Ocean, and the Southern Ocean, making them potentially more vulnerable to ocean acidification. The impact of acidification is being felt globally, but with significant heterogeneity in the temporal and spatial patterns of response due to regional differences in chemistry, circulation, and biology. Coral reefs, which provide trillions of dollars in societal services worldwide, are projected to experience decreased net calcification, a key process in maintaining ecosystem function. Mass mortality events in shellfish hatcheries have also been linked to ocean acidification. For example, pteropods, a pelagic sea snail that is an important prey species for fish such as salmon, cod, and mackerel, have been demonstrated to be especially vulnerable to elevated CO 2 conditions. Ocean acidification is thought to have widespread detrimental impacts on marine organisms and ecosystems including those that support valuable fisheries. This process, known as ocean acidification, is happening more rapidly than at any other time in Earth’s history. On average, open ocean pH has decreased by approximately 0.0018 year −1 over the past 15–30 years. The dissolving of CO 2 acidifies the seawater (lowers pH) and shifts the equilibrium of carbonate species, decreasing carbonate ion and increasing bicarbonate concentration. While this reduces atmospheric CO 2 concentrations, it comes at a cost. Each year, the ocean absorbs approximately 25% of anthropogenic emissions of carbon dioxide (CO 2) to the atmosphere and has absorbed at least 25% of all anthropogenic CO 2 since the industrial revolution. The oceanic carbonate system is going through unprecedented change. Sensors now in development promise the ability to observe multiple carbonate system parameters from a range of vehicles in the near future. Most autonomous platforms observe a single carbonate parameter, which leaves us reliant on the use of empirical relationships to constrain the rest of the carbonate system. New integration of developed sensors on gliders and surface vehicles will increase our coastal and regional observational capability. Our developing network of autonomous carbonate observations is currently targeted at surface ocean CO 2 fluxes and compact ecosystem observatories. The initial large-scale deployment of profiling floats equipped with these new pH sensors in the Southern Ocean has demonstrated the feasibility of a global autonomous open-ocean carbonate observing system.
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The development of versatile pH sensors suitable for both deployment on autonomous vehicles and in compact, fixed ecosystem observatories has been a major development in the field. We summarize recent progress on autonomous observations of ocean carbonate chemistry and the development of a network of sensors capable of observing carbonate processes at multiple temporal and spatial scales.