Description: A detailed survey of a high Arctic fjord (Kongsfjorden, Svalbard),subjected to a large glacier discharge, was carried out from 24 July to 13 August 2016. Field activities addressed the identification ofthe effects of glacier and iceberg melting on the evolution of nutrient, dissolved organic matter and carbonate systems in this coastal marine environment. Complete CTD profiles were collected in 60 marine stations in theinner area of Kongsfjorden, during six oceanographic surveys, by means of CTD downcasts. CTD profiles were acquired with a Seabird 19plus SeaCATprofiler, equipped with a TURNER Cyclops turbidimeter.

Description: Oceanographic data were collected in 60 marine stationsinthe inner area ofKongsfjorden, during six oceanographic surveys (24 July -10 August 2016),by means ofCTD downcastsandbottle sampling.CTD profileswere acquired with a Seabird 19plus SeaCATprofiler,equipped with a TURNER Cyclops turbidimeter. Potential temperature (Θ, ITS-90; °C), salinity (Practical Salinity Scale, PSS-78) and potential density anomaly (σΘ, sigma-theta) were calculated according to McDougall et al. (2010).Seawater samples for chemical analyses were collected using 10 L Niskin bottles at 1-7 depths per station, depending on the depth of the station (9-304 m), withamore intensive sampling of upper layer. Samples for the determination of Dissolved Oxygen (DO;μmol L-1) were drawnin 60 mL borosilicate glass bottles and spiked with Winkler reagents.Samples forthe determination ofmacronutrients (nitrate, NO3-; nitrite, NO2-; reactive silicate, Si(OH)4; orthophosphate, PO43-; μmol L-1), Dissolved Organic Carbon (DOC, μmol L-1) and Nitrogen (DON, μmol L-1) were syringe filtered withprecombusted (450 °C, 4 h) GF/F filters, placed in acid-washed HDPE vials and stored at -20 °C until analysis.Seawater samples for the determination of pH, dissolved inorganic carbon (DIC; μmol kgSW-1) and total alkalinity (TA; μmol kgSW-1) were collected in borosilicate glass bottles. Sample lids were immediately greased (Apiezon L), sealed with positive pressure on the lid, and stored refrigerated (4 °C) in the dark until analysis. The samples were poisoned with 100 μL HgCl2soln. only if they could not be analysed within 24 hour of the collection (Dickson et al., 2007).

Description: Ice samples (1-2 kg) from small icebergs floating in the fjord were collected and returned to the laboratoryin insulated plastic boxes, rinsed with ultra-pure laboratory water and melted in low-density polyethylene bags. The first melt water was discarded, whereas the remaining freshwater was subsampled for the determination of chemical parameters.

Description: Freshwater samples and physical parameterswere also collectedin theglacial drainages surrounding the fjordin 55 sampling points. This included supraglacial streams and proglacial watercourses from the moraines to the coast (0-5 km in length). Temperature and conductivityin freshwaterwere measured with a portable Conductivity-Meter (LF325, WTW). For chemical parameters, a 10 L carboy was submerged in streams until the bubbles were removed. Subsamples were then collected using a silicone tube for the determination of nutrients, DOC, DON, DIC, pH and TA.

Description: A detailed survey of a high Arctic fjord (Kongsfjorden, Svalbard), subjected to a large glacier discharge, was carried out from 24 July to 13 August 2016. Field activities addressed the identification of the effects of glacier and iceberg melting on the evolution of nutrient, dissolved organic matter and carbonate systems in this coastal marine environment. Hydrological (CTD downcasts) and biogeochemical (bottle sampling) data were collected during six oceanographic surveys in the inner area of the fjord, in concomitance to the annual phase of maximum air warming. An extensive sampling was also carried out in all glacier drainage systems located around the fjord and from several iceberg samples, in order to characterize all freshwater loads. The dataset includes hydrological data (T, Sal., density) carbonate chemistry data (pH, DIC, TA) and the concentrations of dissolved oxygen (DO), inorganic nutrients (NO3-, NO2-, NH4+, PO43-, SiO2), dissolved organic matter (DOC, DON) and some micronutrients (Fe, Mn).

Description: The micronutrient iron (Fe) can be transported from marine terminating glaciers to the ocean by icebergs. There are however few observations of iceberg Fe content, and the flux of Fe from icebergs to the offshore surface ocean is poorly constrained. Here we report the dissolved Fe (DFe), total dissolvable Fe (TdFe) and ascorbic acid extractable Fe (FeAsc) sediment content of icebergs from Kongsfjorden, Svalbard. The concentrations of DFe (range 0.63 nM – 536 nM, mean 37 nM, median 6.5 nM) and TdFe (range 46 nM – 57 µM, mean 3.6 µM, median 144 nM) both demonstrated highly heterogeneous distributions and there was no significant correlation between these two fractions. FeAsc (range 0.0042 to 0.12 wt. %) was low compared to both previous measurements in Kongsfjorden and to current estimates of the global mean. FeAsc content per volume ice did however, as expected, show a significant relationship with sediment loading (which ranged from 〈 0.1 – 234 g L-1 of meltwater). In the Arctic, icebergs lose their sediment load faster than ice volume due to the rapid loss of basal ice after calving. We therefore suggest that the loss of basal ice is a potent mechanism for the reduction of mean TdFe and FeAsc per volume of iceberg. Delivery of TdFe and FeAsc to the ocean is thereby biased towards coastal waters where, in Kongsfjorden, DFe (18 ± 17 nM) and TdFe (mean 8.1 µM, median 3.7 µM) concentrations were already elevated.

Description: The ocean is a major sink for anthropogenic carbon dioxide (CO2), with the CO2 uptake causing changes to ocean chemistry. To monitor these changes and provide a chemical background for biological and biogeochemical studies, high quality partial pressure of CO2 (pCO2) sensors are required, with suitable accuracy and precision for ocean measurements. Optodes have the potential to measure in situ pCO2 without the need for wet chemicals or bulky gas equilibration chambers that are typically used in pCO2 systems. However, optodes are still in an early developmental stage compared to more established equilibrator-based pCO2 systems. In this study, we performed a laboratory-based characterization of a time-domain dual lifetime referencing pCO2 optode system. The pCO2 optode spot was illuminated with low intensity light (0.2 mA, 0.72 mW) to minimize spot photobleaching. The spot was calibrated using an experimental gas calibration rig prior to deployment, with a determined response time (τ63) of 50 s at 25°C. The pCO2 optode was deployed as an autonomous shipboard underway system across the high latitude North Atlantic Ocean with a resolution of ca.10 measurements per hour. The optode data was validated with a secondary shipboard equilibrator-based infrared pCO2 instrument, and pCO2 calculated from discrete samples of dissolved inorganic carbon and total alkalinity. Further verification of the pCO2 optode data was achieved using complimentary variables such as nutrients and dissolved oxygen. The shipboard precision of the pCO2 sensor was 9.5 μatm determined both from repeat measurements of certified reference materials and from the standard deviation of seawater measurements while on station. Finally, the optode deployment data was used to evaluate the physical and biogeochemical controls on pCO2.

Description: The trace metal iron (Fe) is an essential micronutrient for phytoplankton growth and limits, or co-limits primary production across much of the world's surface ocean. Iron is a redox sensitive element, with Fe(II) and Fe(III) co-existing in natural waters. Whilst Fe(II) is the most soluble form, it is also transient with rapid oxidation rates in oxic seawater. Measurements of Fe(II) are therefore preferably undertaken in situ. For this purpose an autonomous wet chemical analyzer based on lab-on-chip technology was developed for the in situ determination of the concentration of dissolved (〈0.45 μm) Fe species (Fe(II) and labile Fe) suitable for deployments in a wide range of aquatic environments. The spectrophotometric approach utilizes a buffered ferrozine solution and a ferrozine/ascorbic acid mixture for Fe(II) and labile Fe(III) analyses, respectively. Diffusive mixing, color development and spectrophotometric detection take place in three separate flow cells with different lengths such that the analyzer can measure a broad concentration range from low nM to several μM of Fe, depending on the desired application. A detection limit of 1.9 nM Fe was found. The microfluidic analyzer was tested in situ for nine days in shallow waters in the Kiel Fjord (Germany) along with other sensors as a part of the SenseOCEAN EU-project. The analyzer's performance under natural conditions was assessed with discrete samples collected and processed according to GEOTRACES protocol [acidified to pH 〈 2 and analyzed via inductively coupled plasma mass spectrometry (ICP-MS)]. The mechanical performance of the analyzer over the nine day period was good (consistent high precision of Fe(II) and Fe(III) standards with a standard deviation of 2.7% (n = 214) and 1.9% (n = 217), respectively, and successful completion of every programmed data point). However, total dissolved Fe was consistently low compared to ICP-MS data. Recoveries between 16 and 75% were observed, indicating that the analyzer does not measure a significant fraction of natural dissolved Fe species in coastal seawater. It is suggested that an acidification step would be necessary in order to ensure that the analyzer derived total dissolved Fe concentration is reproducible and consistent with discrete values.

Description: The oceans are a major sink for anthropogenic atmospheric carbon dioxide, and the uptake causes changes to the marine carbonate system and has wide ranging effects on flora and fauna. It is crucial to develop analytical systems that allow us to follow the increase in oceanic pCO(2) and corresponding reduction in pH. Miniaturised sensor systems using immobilised fluorescence indicator spots are attractive for this purpose because of their simple design and low power requirements. The technology is increasingly used for oceanic dissolved oxygen measurements. We present a detailed method on the use of immobilised fluorescence indicator spots to determine pH in ocean waters across the pH range 7.6-8.2. We characterised temperature (-0.046 pH/degrees C from 5 to 25 degrees C) and salinity dependences (-0.01 pH/psu over 5-35), and performed a preliminary investigation into the influence of chlorophyll on the pH measurement. The apparent pK(a) of the sensor spots was 6.93 at 20 degrees C. A drift of 0.00014 R (ca. 0.0004 pH, at 25 degrees C, salinity 35) was observed over a 3 day period in a laboratory based drift experiment. We achieved a precision of 0.0074 pH units, and observed a drift of 0.06 pH units during a test deployment of 5 week duration in the Southern Ocean as an under way surface ocean sensor, which was corrected for using certified reference materials. The temperature and salinity dependences were accounted for with the algorithm, R = (0.00034 - 0.17.pH + 0.15.S-2 + 0.0067.T - 0.0084.S) . 1.075. This study provides a first step towards a pH optode system suitable for autonomous deployment. The use of a short duration low power illumination (LED current 0.2 mA, 5 mu s illumination time) improved the lifetime and precision of the spot. Further improvements to the pH indicator spot operations include regular application of certified reference materials for drift correction and cross-calibration against a spectrophotometric pH system. Desirable future developments should involve novel fluorescence spots with improved response time and apparent pK(a) values closer to the pH of surface ocean waters.