Approaches and tools to manipulate the carbonate chemistry

Although the chemistry of ocean acidifi cation is very well understood (see chapter 1), its impact on marine organisms and ecosystems remains poorly known. The biological response to ocean acidifi cation is a recent field of research, the fi rst purposeful experiments have only been carried out as late as the 1980s (Agegian, 1985) and most were not performed until the late 1990s. The potentially dire consequences of ocean acidifi cation have attracted the interest of scientists and students with a limited knowledge of the carbonate chemistry and its experimental manipulation. Perturbation experiments are one of the key approaches used to investigate the biological response to elevated p(CO2). Such experiments are based on measurements of physiological or metabolic processes in organisms and communities exposed to seawater with normal and altered carbonate chemistry. The basics of the carbonate chemistry must be understood to perform meaningful CO2 perturbation experiments (see chapter 1). Briefl y, the marine carbonate system considers € CO2 ∗(aq) [the sum of CO2 and H2CO3], € HCO3 −, € CO3 2−, H+, € OH− , and several weak acid-base systems of which borate-boric acid (€ B(OH)4 − , B(OH)3) is the most important. As discussed by Dickson (chapter 1), if two components of the carbonate chemistry are known, all the other components can be calculated for seawater with typical nutrient concentrations at given temperature, salinity, and pressure. One of the possible pairs is of particular interest because both components can be measured with precision, accuracy, and are conservative in the sense that their concentrations do not change with temperature or pressure. Dissolved inorganic carbon (DIC) is the sum of all dissolved inorganic carbon species while total alkalinity (AT) equals € [HCO3 − ] + 2 € [CO3 2− ] + € [B(OH)4 − ] + € [OH− ] - [H+] + minor components, and refl ects the excess of proton acceptors over proton donors with respect to a zero level of protons (see chapter 1 for a detailed defi nition). AT is determined by the titration of seawater with a strong acid and thus can also be regarded as a measure of the buffering capacity. Any changes in any single component of the carbonate system will lead to changes in several, if not all, other components. In other words, it is not possible to vary a single component of the carbonate system while keeping all other components constant. This interdependency in the carbonate system is important to consider when performing CO2 perturbation experiments. To adjust seawater to different p(CO2) levels, the carbonate system can be manipulated in various ways that usually involve changes in AT or DIC. The goal of this chapter is (1) to examine the benefi ts and drawbacks of various manipulation methods used to date and (2) to provide a simple software package to assist the design of perturbation experiments

A dataset for investigating socio-ecological changes in Arctic fjords

The collection of in situ data is generally a costly process, with the Arctic being no exception. Indeed, there has been a perception that the Arctic is lacking in situ sampling; however, after many years of concerted effort and international collaboration, the Arctic is now rather well sampled, with many cruise expeditions every year. For example, the GLODAP (Global Ocean Data Analysis Project) product has a greater density of in situ sampling points within the Arctic than along the Equator. While this is useful for open-ocean processes, the fjords of the Arctic, which serve as crucially important intersections of terrestrial, coastal, and marine processes, are sampled in a much more ad hoc process. This is not to say they are not well sampled but rather that the data are more difficult to source and combine for further analysis. It was therefore noted that the fjords of the Arctic are lacking in FAIR (findable, accessible, interoperable, and reusable) data. To address this issue, a single dataset has been created from publicly available, predominantly in situ data from seven study sites in Svalbard and Greenland. After finding and accessing the data from a number of online platforms, they were amalgamated into a single project-wide standard, ensuring their interoperability. The dataset was then uploaded to PANGAEA so that it can be findable and reusable in the future. The focus of the data collection was driven by the key drivers of change in Arctic fjords identified in a companion review paper. To demonstrate the usability of this dataset, an analysis of the relationship between the different drivers was performed. Via the use of an Arctic biogeochemical model, these relationships were projected forward to 2100 via Representative Carbon Pathways (RCPs) 2.6, 4.5, and 8.5. This dataset is a work in progress, and as new datasets containing the relevant key drivers are released, they will be added to an updated version planned for the middle of 2024. The dataset (Schlegel and Gattuso, 2022) is available on PANGAEA at https://doi.org/10.1594/PANGAEA.953115. A live version is available at the FACE-IT WP1 site and can be accessed by clicking the “Data access” tab: https://face-it-project.github.io/WP1/ (last access: 17 August 2023).</p

Preface "Arctic ocean acidification: pelagic ecosystem and biogeochemical responses during a mesocosm study"

The growing evidence of potential biological impacts of ocean acidification affirms that this global change phenomenon may pose a serious threat to marine organisms and ecosystems. Whilst ocean acidification will occur everywhere, it will happen more rapidly in some regions than in others. Due to the high CO2 solubility in the cold surface waters of high-latitude seas, these areas are expected to experience the strongest changes in seawater chemistry due to ocean acidification. This will be most pronounced in the Arctic Ocean. If atmospheric pCO2 levels continue to rise at current rates, about 10% of the Arctic surface waters will be corrosive for aragonite by 2018 (Steinacher et al., 2009). By 2050 one-half of the Arctic Ocean will be sub-saturated with respect to aragonite. By the end of this century corrosive conditions are projected to have spread over the entire Arctic Ocean (Steinacher et al., 2009). In view of these rapid changes in seawater chemistry, marine organisms and ecosystems in the Arctic are considered particularly vulnerable to ocean acidification. With this in mind, the European Project on Ocean Acidification (EPOCA) chose the Arctic Ocean as one of its focal areas of research

Synthesis, x-ray structure and anion binding properties of a cryptand-like hybrid calixpyrrole

The novel cryptand in/out-3, containing two tripyrrolemethane units briged by three 1,3- diisopropylidenbenzene arms was readily synthesized by a convergent three-step synthesis. It binds fluoride by inclusion with excellent selectivity with respect to a number of other tested anions. The structure of the free receptor and that of its fluoride complex were investigated in solution by NMR spectroscopy. The solid state X-ray structure of the free cryptand 3 was also determined

Impact of ocean acidification on a key Arctic pelagic mollusc (Limacina helicina)

Thecosome pteropods (shelled pelagic molluscs) can play an important role in the food web of various ecosystems and play a key role in the cycling of carbon and carbonate. Since they harbor an aragonitic shell, they could be very sensitive to ocean acidification driven by the increase of anthropogenic CO2 emissions. The impact of changes in the carbonate chemistry was investigated on Limacina helicina, a key species of Arctic ecosystems. Pteropods were kept in culture under controlled pH conditions corresponding to pCO2 levels of 350 and 760 μatm. Calcification was estimated using a fluorochrome and the radioisotope 45Ca. It exhibits a 28% decrease at the pH value expected for 2100 compared to the present pH value. This result supports the concern for the future of pteropods in a high-CO2 world, as well as of those species dependent upon them as a food resource. A decline of their populations would likely cause dramatic changes to the structure, function and services of polar ecosystems

Evaluation of data-based estimates of anthropogenic carbon in the Arctic Ocean

The Arctic Ocean is particularly vulnerable to ocean acidification, a process that is mainly driven by the uptake of anthropogenic carbon (Cant) from the atmosphere. Although Cant concentrations cannot be measured directly in the ocean, they have been estimated using data-based methods such as the transient time distribution (TTD) approach, which characterizes the ventilation of water masses with inert transient tracers, such as CFC-12. Here, we evaluate the TTD approach in the Arctic Ocean using an eddying ocean model as a test bed. When the TTD approach is applied to simulated CFC-12 in that model, it underestimates the same model's directly simulated Cant concentrations by up to 12%, a bias that stems from its idealized assumption of gas equilibrium between atmosphere and surface water, both for CFC-12 and anthropogenic CO2. Unlike the idealized assumption, the simulated partial pressure of CFC-12 (pCFC-12) in Arctic surface waters is undersaturated relative to that in the atmosphere in regions and times of deep-water formation, while the simulated equivalent for Cant is supersaturated. After accounting for the TTD approach's negative bias, the total amount of Cant in the Arctic Ocean in 2005 increases by 8% to 3.3 ± 0.3 Pg C. By combining the adjusted TTD approach with scenarios of future atmospheric CO2, it is estimated that all Arctic waters, from surface to depth, would become corrosive to aragonite by the middle of the next century even if atmospheric CO2 could be stabilized at 540 ppm

Effect of CO2 enrichment on bacterial metabolism in an Arctic fjord

he anthropogenic increase of carbon dioxide (CO2) alters the seawater carbonate chemistry, with a decline of pH and an increase in the partial pressure of CO2 (pCO2). Although bacteria play a major role in carbon cycling, little is known about the impact of rising pCO2 on bacterial carbon metabolism, especially for natural bacterial communities. In this study, we investigated the effect of rising pCO2 on bacterial production (BP), bacterial respiration (BR) and bacterial carbon metabolism during a mesocosm experiment performed in Kongsfjorden (Svalbard) in 2010. Nine mesocosms with pCO2 levels ranging from ca. 180 to 1400 μatm were deployed in the fjord and monitored for 30 days. Generally BP gradually decreased in all mesocosms in an initial phase, showed a large (3.6-fold average) but temporary increase on day 10, and increased slightly after inorganic nutrient addition. Over the wide range of pCO2 investigated, the patterns in BP and growth rate of bulk and free-living communities were generally similar over time. However, BP of the bulk community significantly decreased with increasing pCO2 after nutrient addition (day 14). In addition, increasing pCO2 enhanced the leucine to thymidine (Leu : TdR) ratio at the end of experiment, suggesting that pCO2 may alter the growth balance of bacteria. Stepwise multiple regression analysis suggests that multiple factors, including pCO2, explained the changes of BP, growth rate and Leu : TdR ratio at the end of the experiment. In contrast to BP, no clear trend and effect of changes of pCO2 was observed for BR, bacterial carbon demand and bacterial growth efficiency. Overall, the results suggest that changes in pCO2 potentially influence bacterial production, growth rate and growth balance rather than the conversion of dissolved organic matter into CO2

Hot, Sour and Breathless – Ocean under Stress.

ISBN 978-0-9519618-6-

Technical note: An autonomous flow-through salinity and temperature perturbation mesocosm system for multi-stressor experiments

The rapid environmental changes in aquatic systems as a result of anthropogenic forcings are creating a multitude of challenging conditions for organisms and communities. The need to better understand the interaction of environmental stressors now, and in the future, is fundamental to determining the response of ecosystems to these perturbations. This work describes an automated ex situ mesocosm perturbation system that can manipulate several variables of aquatic media in a controlled setting. This perturbation system was deployed in Kongsfjorden (Svalbard); within this system, ambient water from the fjord was heated and mixed with freshwater in a multifactorial design to investigate the response of mixed-kelp communities in mesocosms to projected future Arctic conditions. The system employed an automated dynamic offset scenario in which a nominal temperature increase was programmed as a set value above real-time ambient conditions in order to simulate future warming. A freshening component was applied in a similar manner: a decrease in salinity was coupled to track the temperature offset based on a temperature–salinity relationship in the fjord. The system functioned as an automated mixing manifold that adjusted flow rates of warmed and chilled ambient seawater, with unmanipulated ambient seawater and freshwater delivered as a single source of mixed media to individual mesocosms. These conditions were maintained via continuously measured temperature and salinity in 12 mesocosms (1 control and 3 treatments, all in triplicate) for 54 d. System regulation was robust, as median deviations from nominal conditions were &lt; 0.15 for both temperature (∘C) and salinity across the three replicates per treatment. Regulation further improved during a second deployment that mimicked three marine heat wave scenarios in which a dynamic temperature regulation held median deviations to &lt; 0.036 ∘C from the nominal value for all treatment conditions and replicates. This perturbation system has the potential to be implemented across a wide range of conditions to test single or multi-stressor drivers (e.g., increased temperature, freshening, and high CO2) while maintaining natural variability. The automated and independent control for each experimental unit (if desired) provides a large breadth of versatility with respect to experimental design.</p