Medusa–Aqua system: simultaneous measurement and evaluation of novel potential halogenated transient tracers HCFCs, HFCs, and PFCs in the ocean

Abstract

Abstract. This study evaluates the potential usefulness of the halogenated compounds HCFC-22, HCFC-141b, HCFC-142b, HFC-134a, HFC-125, HFC-23, PFC-14, and PFC-116 as oceanographic transient tracers to better constrain ocean ventilation processes. We do this mainly in terms of four aspects of the characteristics of the potential tracers: input function (including atmospheric history and historical surface saturation), seawater solubility, feasibility of measurement, and stability in seawater; of these, atmospheric history and seawater solubility have been investigated in previous work. For the latter two aspects, we collected seawater samples and modified an established analytical technique for the Medusa–Aqua system to simultaneously measure these compounds. HCFC-22, HCFC-141b, HCFC-142b, HFC-134a, and HFC-125 have been measured in depth profiles in the Mediterranean Sea for the first time and for reproducibility in the Baltic Sea. We found that the historical surface saturation of halogenated transient tracers in the Mediterranean Sea is estimated to have been nearly constant at 94 % based on historical data. Of the investigated compounds, HCFC-142b, HCFC-141b, and HFC-134a are found to currently be the most promising transient tracers in the ocean. The compounds that have the greatest potential as future tracers are PFC-14 and PFC-116, mainly hampered by the low solubility in seawater that creates challenging analytical conditions, i.e., low concentrations. HCFC-22 is found to be likely unstable in warm seawater, which compromises the potential as an oceanic transient tracer, although it is possibly useful in colder water. For the compounds HFC-125 and HFC-23, we were not able to fully evaluate their potential as tracers due to inconclusive results, especially regarding their solubility and stability in seawater, but also with regard to potential analytical challenges. On the other hand, HFC-125, HFC-23, and HCFC-22 might not need to be considered because there are alternative tracers with similar input histories that are better suited as transient tracers.