Changes may be occurring in the carbonate chemistry of fjords due to natural and anthropogenic disturbance of major freshwater sources. We present a high‐frequency time series study of seasonal pH and CO2 partial pressure (pCO2) in a north Patagonian fjord with a focus on changes in freshwater inflows and biological processes. To do this, we monitored pH and pCO2 in situ, along with river streamflow, salinity, temperature, and dissolved oxygen (DO) in the Reloncaví Fjord (41.5°S) for a full year (January to December 2015). Strong seasonal variability was observed in the pCO2, pH, and DO of the fjord's surface waters. During the summer, pCO2 reached its annual minimum (range: 187–571 μatm) and pH its maximum (range: 7.98–8.24), coinciding with lower freshwater inflows (204–307 m3/s) and high DO (280–378 μmol/kg), as well as aragonite saturation states (ΩArag) higher than 1. In contrast, in winter, pCO2 ranged from 461–1,008 μatm and pH from 7.57–8.03, coinciding with high freshwater inflows (1,049–1,402 m3/s), lower oxygen (216–348 μmol/kg), and constant undersaturation of ΩArag. Reloncaví Fjord had an annual air‐water CO2 flux of 0.716 ± 2.54 mol·m−2·year−1 during 2015 and thus acted as a low emission system. The annual cycle was mainly governed by seasonal changes in biological processes that enhanced the shift from a CO2 sink in late spring and summer, caused by high primary production rates, to a CO2 source during the rest of the year caused by high community respiration due to allochthonous organic carbon inputs.

Abstract. Following the eruption of the Calbuco volcano in April 2015, an extensive ash plume spread across northern Patagonia and into the southeast Pacific and southwest Atlantic oceans. Here, we report on field surveys conducted in the coastal region receiving the highest ash load following the eruption (Reloncaví Fjord). The fortuitous location of a long-term monitoring station in Reloncaví Fjord provided data to evaluate inshore phytoplankton bloom dynamics and carbonate chemistry during April–May 2015. Satellite-derived chlorophyll a measurements over the ocean regions affected by the ash plume in May 2015 were obtained to determine the spatial–temporal gradients in the offshore phytoplankton response to ash. Additionally, leaching experiments were performed to quantify the release from ash into solution of total alkalinity, trace elements (dissolved Fe, Mn, Pb, Co, Cu, Ni and Cd) and major ions (F−, Cl−, SO42-, NO3-, Li+, Na+, NH4+, K+, Mg2+ and Ca2+). Within Reloncaví Fjord, integrated peak diatom abundances during the May 2015 austral bloom were approximately 2–4 times higher than usual (up to 1.4 × 1011 cells m−2, integrated to 15 m depth), with the bloom intensity perhaps moderated due to high ash loadings in the 2 weeks following the eruption. Any mechanistic link between ash deposition and the Reloncaví diatom bloom can, however, only be speculated on due to the lack of data immediately preceding and following the eruption. In the offshore southeast Pacific, a short-duration phytoplankton bloom corresponded closely in space and time to the maximum observed ash plume, potentially in response to Fe fertilisation of a region where phytoplankton growth is typically Fe limited at this time of year. Conversely, no clear fertilisation on the same timescale was found in the area subject to an ash plume over the southwest Atlantic where the availability of fixed nitrogen is thought to limit phytoplankton growth. This was consistent with no significant release of fixed nitrogen (NOx or NH4) from Calbuco ash. In addition to the release of nanomolar concentrations of dissolved Fe from ash suspended in seawater, it was observed that low loadings (< 5 mg L−1) of ash were an unusually prolific source of Fe(II) into chilled seawater (up to 1.0 µmol Fe g−1), producing a pulse of Fe(II) typically released mainly during the first minute after addition to seawater. This release would not be detected (as Fe(II) or dissolved Fe) following standard leaching protocols at room temperature. A pulse of Fe(II) release upon addition of Calbuco ash to seawater made it an unusually efficient dissolved Fe source. The fraction of dissolved Fe released as Fe(II) from Calbuco ash (∼ 18 %–38 %) was roughly comparable to literature values for Fe released into seawater from aerosols collected over the Pacific Ocean following long-range atmospheric transport.

The biogeochemical dynamics of fjords in the southeastern Pacific Ocean are strongly influenced by hydrological and oceanographic processes occurring at a seasonal scale. In this study, we describe the role of hydrographic forcing on the seasonal variability of the carbonate system of the Sub-Antarctic glacial fjord, Seno Ballena, in the Strait of Magellan (53°S). Biogeochemical variables were measured in 2018 during three seasonal hydrographic cruises (fall, winter and spring) and from a high-frequency pCO2-pH mooring for 10 months at 10 ± 1 m depth in the fjord. The hydrographic data showed that freshwater input from the glacier influenced the adjacent surface layer of the fjord and forced the development of undersaturated CO2 (&lt; 400 μatm) and low aragonite saturation state (ΩAr &lt; 1) water. During spring, the surface water had relatively low pCO2 (mean = 365, range: 167 - 471 μatm), high pH (mean = 8.1 on the total proton concentration scale, range: 8.0 - 8.3), and high ΩAr (mean = 1.6, range: 1.3 - 4.0). Concurrent measurements of phytoplankton biomass and nutrient conditions during spring indicated that the periods of lower pCO2 values corresponded to higher phytoplankton photosynthesis rates, resulting from autochthonous nutrient input and vertical mixing. In contrast, higher values of pCO2 (range: 365 – 433 μatm) and relatively lower values of pHT (range: 8.0 – 8.1) and ΩAr (range: 0.9 – 2.0) were recorded in cold surface waters during winter and fall. The naturally low freshwater carbonate ion concentrations diluted the carbonate ion concentrations in seawater and decreased the calcium carbonate saturation of the fjord. In spring, at 10 m depth, higher primary productivity caused a relative increase in ΩAr and pHT. Assuming global climate change will bring further glacier retreat and ocean acidification, this study represents important advances in our understanding of glacier meltwater processes on CO2 dynamics in glacier–fjord systems.