Description: Highlights: • Three different types of pCO2 sensors detected sedimentary artificial CO2 leaks in the water column. • Distribution of leaked CO2 in the water column featured high temporal and spatial heterogeneity. • Clear effect of CO2 leakage on the water column was visible only at high flow rates and low tides. • Fast recovery of the water column pCO2 was observed after the CO2 release was stopped. • Multivariate statistics can help to distinguish between anthropogenic and natural CO2 sources. Abstract: This work is focused on results from a recent controlled sub-seabed in situ carbon dioxide (CO2) release experiment carried out during May–October 2012 in Ardmucknish Bay on the Scottish west coast. Three types of pCO2 sensors (fluorescence, NDIR and ISFET-based technologies) were used in combination with multiparameter instruments measuring oxygen, temperature, salinity and currents in the water column at the epicentre of release and further away. It was shown that distribution of seafloor CO2 emissions features high spatial and temporal heterogeneity. The highest pCO2 values (∼1250 μatm) were detected at low tide around a bubble stream and within centimetres distance from the seafloor. Further up in the water column, 30–100 cm above the seabed, the gradients decreased, but continued to indicate elevated pCO2 at the epicentre of release throughout the injection campaign with the peak values between 400 and 740 μatm. High-frequency parallel measurements from two instruments placed within 1 m from each other, relocation of one of the instruments at the release site and 2D horizontal mapping of the release and control sites confirmed a localized impact from CO2 emissions. Observed effects on the water column were temporary and post-injection recovery took 〈7 days. A multivariate statistical approach was used to recognize the periods when the system was dominated by natural forcing with strong correlation between variation in pCO2 and O2, and when it was influenced by purposefully released CO2. Use of a hydrodynamic circulation model, calibrated with in situ data, was crucial to establishing background conditions in this complex and dynamic shallow water system.

Description: We investigated the effect of hydrostatic pressure of up to 6000 dbar on Aanderaa and Sea-Bird oxygen optodes both in the laboratory and in the field. The overall pressure response is a reduction in the O2 reading by 3 – 4 % per 1000 dbar which is closely linear with pressure and increases with temperature. Closer inspection reveals two superimposed processes with opposite effect: an O2-independent pressure response on the luminophore which increases optode O2 readings and an O2-dependent change in luminescence quenching which decreases optode O2 readings. The latter process dominates and is mainly due to a shift in the equilibrium between sensing membrane and sea water under elevated pressures. If only the dominant O2-dependent process is considered, Aanderaa and Sea-Bird optodes differ in their pressure response. Compensation of the O2-independent process, however, yields a uniform O2 dependence for Aanderaa optodes with standard foil and fast-response foil as well as Sea-Bird optodes. A new scheme to calculate optode O2 from raw data is proposed to account for the two processes. The overall uncertainty of the optode pressure correction amounts to 0.3 % per 1000 dbar, mainly due to variability between sensors.

Description: It has been speculated that macrophytes beds might act as a refuge for calcifiers from ocean acidification. In the shallow nearshores of the western Kiel Bay (Baltic Sea), mussel and seagrass beds are interlacing, forming a mosaic habitat. Naturally, the diverse physiological activities of seagrasses and mussels are affected by seawater carbonate chemistry and they locally modify it in return. Calcification by shellfishes is sensitive to seawater acidity; therefore the photosynthetic activity of seagrasses in confined shallow waters creates favorable chemical conditions to calcification at daytime but turn the habitat less favorable or even corrosive to shells at night. In contrast, mussel respiration releases CO2, turning the environment more favorable for photosynthesis by adjacent seagrasses. At the end of summer, these dynamics are altered by the invasion of high pCO2/low O2 coming from the deep water of the Bay. However, it is in summer that mussel spats settle on the leaves of seagrasses until migrating to the permanent habitat where they will grow adult. These early life phases (larvae/spats) are considered as most sensitive with regard to seawater acidity. So far, the dynamics of CO2 have never been continuously measured during this key period of the year, mostly due to the technological limitations. In this project we used a combination of state-of-the-art technologies and discrete sampling to obtain high-resolution time-series of pCO2 and O2 at the interface between a seagrass and a mussel patch in Kiel Bay in August and September 2013. From these, we derive the entire carbonate chemistry using statistical models. We found the monthly average pCO2 more than 50 % (approx. 640 μatm for August and September) above atmospheric equilibrium right above the mussel patch together with large diel variations of pCO2 within 24 h: 887 ± 331 μatm in August and 742 ± 281 μatm in September (mean ± SD). We observed important daily corrosiveness for calcium carbonates (Ωarag and Ωcalc 〈 1) centered on sunrise. On the positive side, the investigated habitat never suffered from hypoxia during the study period. We emphasize the need for more experiments on the impact of these acidic conditions on (juvenile) mussels with a focus on the distinct day-night variations observed.

Description: Report on the network enhancement project, this will document (a) extension of network coverage to South Atlantic; (b) evaluation of improved EOV carbonate system; and (c) re-assessment of instrumentation

Description: Validated prototypes of new and enhanced biogeochemical and biological sensors and instruments. Validation will be undertaken in the laboratory, in test scenarios, and by deployment in operational conditions