ALBERT

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: Certification of trace metals in seawater certified reference materials (CRMs) NASS-7 and CASS-6 is described. At the National Research Council Canada (NRC), column separation was performed to remove the seawater matrix prior to the determination of Cd, Cr, Cu, Fe, Pb, Mn, Mo, Ni, U, V, and Zn, whereas As was directly measured in 10-fold diluted seawater samples, and B was directly measured in 200-fold diluted seawater samples. High-resolution inductively coupled plasma mass spectrometry (HR-ICPMS) was used for elemental analyses, with double isotope dilution for the accurate determination of B, Cd, Cr, Cu, Fe, Pb, Mo, Ni, U, and Zn in seawater NASS-7 and CASS-6, and standard addition calibration for As, Co, Mn, and V. In addition, all analytes were measured using standard addition calibration with triple quadrupole (QQQ)-ICPMS to provide a second set of data at NRC. Expert laboratories worldwide were invited to contribute data to the certification of trace metals in NASS-7 and CASS-6. Various analytical methods were employed by participants including column separation, co-precipitation, and simple dilution coupled to ICPMS detection or flow injection analysis coupled to chemiluminescence detection, with use of double isotope dilution calibration, matrix matching external calibration, and standard addition calibration. Results presented in this study show that majority of laboratories have demonstrated their measurement capabilities for the accurate determination of trace metals in seawater. As a result of this comparison, certified/reference values and associated uncertainties were assigned for 14 elements in seawater CRMs NASS-7 and CASS-6, suitable for the validation of methods used for seawater analysis.

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: In the surface ocean, microorganisms are both a source of extracellular H2O2 and, via the production of H2O2 destroying enzymes, also one of the main H2O2 sinks. Within microbial communities, H2O2 sources and sinks may be unevenly distributed and thus microbial community structure could influence ambient extracellular H2O2 concentrations. Yet the biogeochemical cycling of H2O2 and other reactive oxygen species (ROS) is rarely investigated at the community level. Here, we present a time series of H2O2 concentrations during a 28-day mesocosm experiment where a pCO2 gradient (400–1,450 μatm) was applied to subtropical North Atlantic waters. Pronounced changes in H2O2 concentration were observed over the duration of the experiment. Initially H2O2 concentrations in all mesocosms were strongly correlated with surface H2O2 concentrations in ambient seawaters outside the mesocosms which ranged from 20 to 92 nM over the experiment duration (Spearman Rank Coefficients 0.79–0.93, p-values 〈 0.001–0.015). After approximately 9 days of incubation however, H2O2 concentrations had increased across all mesocosms, later reaching 〉300 nM in some mesocosms (2–6 fold higher than ambient seawaters). The correlation with ambient H2O2 was then no longer significant (p 〉 0.05) in all treatments. Furthermore, changes in H2O2 could not be correlated with inter-day changes in integrated irradiance. Yet H2O2 concentrations in most mesocosms were inversely correlated with bacterial abundance (negative Spearman Rank Coefficients ranging 0.59–0.94, p-values 〈 0.001–0.03). Our results therefore suggest that ambient H2O2 concentration can be influenced by microbial community structure with shifts toward high bacterial abundance correlated with low extracellular H2O2 concentrations. We also infer that the nature of mesocosm experiment design, i.e., the enclosure of water within open containers at the ocean surface, can strongly influence extracellular H2O2 concentrations. This has potential chemical and biological implications during incubation experiments due to the role of H2O2 as both a stressor to microbial functioning and a reactive component involved in the cycling of numerous chemical species including, for example, trace metals and haloalkanes.

Description: Oceanic uptake of anthropogenic carbon dioxide (CO2) causes pronounced shifts in marine carbonate chemistry and a decrease in seawater pH. Increasing evidence indicates that these changes—summarized by the term ocean acidification (OA)—can significantly affect marine food webs and biogeochemical cycles. However, current scientific knowledge is largely based on laboratory experiments with single species and artificial boundary conditions, whereas studies of natural plankton communities are still relatively rare. Moreover, the few existing community-level studies were mostly conducted in rather eutrophic environments, while less attention has been paid to oligotrophic systems such as the subtropical ocean gyres. Here we report from a recent in situ mesocosm experiment off the coast of Gran Canaria in the eastern subtropical North Atlantic, where we investigated the influence of OA on the ecology and biogeochemistry of plankton communities in oligotrophic waters under close-to-natural conditions. This paper is the first in this Research Topic of Frontiers in Marine Biogeochemistry and provides (1) a detailed overview of the experimental design and important events during our mesocosm campaign, and (2) first insights into the ecological responses of plankton communities to simulated OA over the course of the 62-day experiment. One particular scientific objective of our mesocosm experiment was to investigate how OA impacts might differ between oligotrophic conditions and phases of high biological productivity, which regularly occur in response to upwelling of nutrient-rich deep water in the study region. Therefore, we specifically developed a deep water collection system that allowed us to obtain ~85 m3 of seawater from ~650 m depth. Thereby, we replaced ~20% of each mesocosm's volume with deep water and successfully simulated a deep water upwelling event that induced a pronounced plankton bloom. Our study revealed significant effects of OA on the entire food web, leading to a restructuring of plankton communities that emerged during the oligotrophic phase, and was further amplified during the bloom that developed in response to deep water addition. Such CO2-related shifts in plankton community composition could have consequences for ecosystem productivity, biomass transfer to higher trophic levels, and biogeochemical element cycling of oligotrophic ocean regions.

Description: Dissolved Fe(II) in seawater is deemed an important micronutrient for microbial organisms, but its analysis is challenging due to its transient nature. We conducted a series of Fe(II) method comparison experiments, where spikes of 5 to 31 nM Fe(II) were added to manipulated seawaters with varying dissolved oxygen (37 to 156 μM) concentrations. The observed Fe(II) concentrations from four analytical methods were compared: spectrophotometry with ferrozine, stripping voltammetry, and flow injection analysis using luminol (with, and without, a pre-concentration column). Direct comparisons between the different methods were undertaken from the derived apparent Fe(II) oxidation rate constant (k1). Whilst the two luminol based methods produced the most similar concentrations throughout the experiments, k1 was still subject to a 20–30% discrepancy between them. Contributing factors may have included uncertainty in the calibration curves, and different responses to interferences from Co(II) and humic/fulvic organic material. The difference in measured Fe(II) concentrations between the luminol and ferrozine methods, from 10 min–2 h after the Fe(II) spikes were added, was always relatively large in absolute terms (〉4 nM) and relative to the spike added (〉20% of the initial Fe(II) concentration). k1 derived from ferrozine observed Fe(II) concentrations was 3–80%, and 4–16%, of that derived from luminol observed Fe(II) with, and without, pre-concentration respectively. The poorest comparability of k1 was found after humic/fulvic material was added to raise dissolved organic carbon to 120 μM. A luminol method without pre-concentration then observed Fe(II) to fall below the detection limit (〈0.49 nM) within 10 min of a 17 nM Fe(II) spike addition, yet other methods still observed Fe(II) concentrations of 2.7 to 3.7 nM 30 min later. k1 also diverged accordingly with the ferrozine derived value 4% of that derived from luminol without pre-concentration. These apparent inconsistencies suggest that some inter-dataset differences in measured Fe(II) oxidation rates in natural waters may be attributable to differences in the analytical methods used rather than arising solely from substantial shifts in Fe(II) speciation.

Description: The development of phosphate sensors suitable for long-term in situ deployments in natural waters, is essential to improve our understanding of the distribution, fluxes, and biogeochemical role of this key nutrient in a changing ocean. Here, we describe the optimization of the molybdenum blue method for in situ work using a lab-on-chip (LOC) analyzer and evaluate its performance in the laboratory and at two contrasting field sites. The in situ performance of the LOC sensor is evaluated using hourly time-series data from a 56-day trial in Southampton Water (UK), as well as a month-long deployment in the subtropical oligotrophic waters of Kaneohe Bay (Hawaii, USA). In Kaneohe Bay, where phosphate concentrations were characteristic of the dry season (0.13 ± 0.03 μM, n = 704), the in situ sensor accuracy was 16 ± 12% and a potential diurnal cycle in phosphate concentrations was observed. In Southampton Water, the sensor data (1.02 ± 0.40 μM, n = 1,267) were accurate to ±0.10 μM relative to discrete reference samples. Hourly in situ monitoring revealed striking tidal and storm derived fluctuations in phosphate concentrations in Southampton Water that would not have been captured via discrete sampling. We show the impact of storms on phosphate concentrations in Southampton Water is modulated by the spring-neap tidal cycle and that the 10-fold decline in phosphate concentrations observed during the later stages of the deployment was consistent with the timing of a spring phytoplankton bloom in the English Channel. Under controlled laboratory conditions in a 250 L tank, the sensor demonstrated an accuracy and precision better than 10% irrespective of the salinity (0–30), turbidity (0–100 NTU), colored dissolved organic matter (CDOM) concentration (0–10 mg/L), and temperature (5–20°C) of the water (0.3–13 μM phosphate) being analyzed. This work demonstrates that the LOC technology is mature enough to quantify the influence of stochastic events on nutrient budgets and to elucidate the role of phosphate in regulating phytoplankton productivity and community composition in estuarine and coastal regimes.

Description: Coastal marine environments are contaminated globally with a vast quantity of unexploded ordnance and munitions from intentional disposal. These munitions contain organic explosive compounds as well as a variety of metals, and represent point sources of chemical pollution to marine waters. Most underwater munitions originate from World Wars at the beginning of the twentieth century, and metal munitions housings have been impacted by extensive corrosion over the course of the following decades. As a result, the risk of munitions-related contaminant release to the water column is increasing. The behavior of munitions compounds is well-characterized in terrestrial systems and groundwater, but is only poorly understood in marine systems. Organic explosive compounds, primarily nitroaromatics and nitramines, can be degraded or transformed by a variety of biotic and abiotic mechanisms. These reaction products exhibit a range in biogeochemical characteristics such as sorption by particles and sediments, and variable environmental behavior as a result. The reaction products often exhibit increased toxicity to biological receptors and geochemical controls like sorption can limit this exposure. Environmental samples typically show low concentrations of munitions compounds in water and sediments (on the order of ng/L and μg/kg, respectively), and ecological risk appears generally low. Nonetheless, recent work demonstrates the possibility of sub-lethal genetic and metabolic effects. This review evaluates the state of knowledge on the occurrence, fate, and effect of munition-related chemical contaminants in the marine environment. There remain a number of knowledge gaps that limit our understanding of munitions-related contaminant spread and effect, and the need for additional work is made all the more urgent by increasing risk of release to the environment.