Inorganic Carbon Chemistry Research Articles

Constraining sulfur incorporation in calcite using inorganic precipitation experiments

The sulfur over calcium ratio (S/Ca) in foraminiferal shells was recently proposed as a new and independent proxy for reconstructing marine inorganic carbon chemistry. This new approach assumes that sulfur is incorporated into CaCO3 predominantly in the form of sulfate (SO42−) through lattice substitution for carbonate ions (CO32–), and that S/Ca thus reflects seawater [CO32–]. Although foraminiferal growth experiments validated this approach, field studies showed controversial results suggesting that the potential impact of [CO32–] may be overwritten by one or more parameters. Hence, to better understand the inorganic processes involved, we here investigate S/Ca values in inorganically precipitated CaCO3 (S/Ca(cc)) grown in solutions of CaCl2 − Na2CO3 − Na2SO4 − B(OH)3 − MgCl2. Experimental results indicate the dependence of sulfate partitioning in CaCO3 on the carbon chemistry via changing pH and suggest that faster precipitation rates increase the partition coefficient for sulfur. The S/Ca ratios of our inorganic calcite samples show positive correlation with modelled [CaSO40](aq), but not with the concentration of free SO42− ions. This challenges the traditional model for sulfate incorporation in calcite and implies that the uptake of sulfate potentially occurs via ion-ion pairs rather than being incorporated as single anions. Based on the [Ca2+] dependence via speciation, we here suggest a critical evaluation of this potential proxy. As sulfate complexation seems to control sulfate uptake in inorganic calcite, application as a proxy using foraminiferal calcite may be limited to periods for which seawater chemistry is well-constrained. As foraminiferal calcite growth is modulated by inward Ca2+ flow to the site of calcification coupled to outward H+ pumping, sulfate incorporation as CaSO40 ion-pair in the foraminifer’s shell also provides a mechanistic link for the observed relationship between S/Ca(cc) and [CO32–].

B(OH)4− and CO32− do not compete for incorporation into aragonite in synthetic precipitations at pHtotal 8.20 and 8.41 but do compete at pHtotal 8.59

Coral skeletal B/Ca (effectively B/CO32–), in combination with boron isotopic composition (δ11B), has been used to reconstruct the dissolved inorganic carbon chemistry of coral calcification media and to explore the biomineralisation process and its response to ocean acidification. This approach assumes that B(OH)4−, the B species incorporated into aragonite, competes with dissolved inorganic carbon species for inclusion in the mineral lattice. In this study we precipitated aragonite from seawater in vitro under conditions that simulate the compositions of the calcification media used to build tropical coral skeletons. To deconvolve the effects of pH and [CO32–] on boron incorporation we conducted multiple experiments at constant [CO32–] but variable pH and at constant pH but variable [CO32–], both in the absence and presence of common coral skeletal amino acids. Large changes in solution [CO32–], from < 400 to >1000 µmol kg−1, or in precipitation rate, have no significant effect on aragonite B/Ca at pHtotal of 8.20 and 8.41. A significant inverse relationship is observed between solution [CO32–] and aragonite B/Ca at pHtotal = 8.59. Aragonite B/Ca is positively correlated with seawater pH across precipitations conducted at multiple pH but this relationship is driven by the effect of pH on the abundance of B(OH)4– in seawater. Glutamic acid and glycine enhance the incorporation of B in aragonite but aspartic acid has no measurable effect. Normalising aragonite B/Ca to solution [B(OH)4–] creates KDB(OH)4− which do not vary significantly between pH treatments. This implies that B(OH)4– and CO32– do not compete with each other for inclusion in the aragonite lattice at pHtotal 8.20 and 8.41. Only at high pH (8.59), when [B(OH)4–] is high, do we observe evidence to suggest that the 2 anions compete to be incorporated into the lattice. These high pH conditions represent the uppermost limits reliably measured in the calcification media of tropical corals cultured under present day conditions, suggesting that skeletal B/Ca may not reflect the calcification media dissolved inorganic carbon chemistry in all modern day corals.

The annual update GLODAPv2.2023: the global interior ocean biogeochemical data product

Abstract. The Global Ocean Data Analysis Project (GLODAP) is a synthesis effort providing regular compilations of surface to bottom ocean biogeochemical bottle data, with an emphasis on seawater inorganic carbon chemistry and related variables determined through chemical analysis of seawater samples. GLODAPv2.2023 is an update of the previous version, GLODAPv2.2022 (Lauvset et al., 2022). The major changes are as follows: data from 23 new cruises were added. In addition, a number of changes were made to the data included in GLODAPv2.2022. GLODAPv2.2023 includes measurements from more than 1.4 million water samples from the global oceans collected on 1108 cruises. The data for the now 13 GLODAP core variables (salinity, oxygen, nitrate, silicate, phosphate, dissolved inorganic carbon, total alkalinity, pH, chlorofluorocarbon-11 (CFC-11), CFC-12, CFC-113, CCl4, and SF6) have undergone extensive quality control with a focus on the systematic evaluation of bias. The data are available in two formats: (i) as submitted by the data originator but converted to World Ocean Circulation Experiment (WOCE) exchange format and (ii) as a merged data product with adjustments applied to minimize bias. For the present annual update, adjustments for the 23 new cruises were derived by comparing those data with the data from the 1085 quality-controlled cruises in the GLODAPv2.2022 data product using crossover analysis. SF6 data from all cruises were evaluated by comparison with CFC-12 data measured on the same cruises. For nutrients and ocean carbon dioxide (CO2), chemistry comparisons to estimates based on empirical algorithms provided additional context for adjustment decisions. The adjustments that we applied are intended to remove potential biases from errors related to measurement, calibration, and data-handling practices without removing known or likely time trends or variations in the variables evaluated. The compiled and adjusted data product is believed to be consistent to better than 0.005 in salinity, 1 % in oxygen, 2 % in nitrate, 2 % in silicate, 2 % in phosphate, 4 µmol kg−1 in dissolved inorganic carbon, 4 µmol kg−1 in total alkalinity, 0.01–0.02 in pH (depending on region), and 5 % in the halogenated transient tracers. The other variables included in the compilation, such as isotopic tracers and discrete CO2 fugacity (fCO2), were not subjected to bias comparison or adjustments. The original data, their documentation, and DOI codes are available at the Ocean Carbon and Acidification Data System of NOAA National Centers for Environmental Information (NCEI), which also provides access to the merged data product. This is provided as a single global file and as four regional ones – the Arctic, Atlantic, Indian, and Pacific oceans – under https://doi.org/10.25921/zyrq-ht66 (Lauvset et al., 2023). These bias-adjusted product files also include significant ancillary and approximated data, which were obtained by interpolation of, or calculation from, measured data. This living data update documents the GLODAPv2.2023 methods and provides a broad overview of the secondary quality control procedures and results.

A decade of marine inorganic carbon chemistry observations in the northern Gulf of Alaska – insights into an environment in transition

Abstract. As elsewhere in the global ocean, the Gulf of Alaska is experiencing the rapid onset of ocean acidification (OA) driven by oceanic absorption of anthropogenic emissions of carbon dioxide from the atmosphere. In support of OA research and monitoring, we present here a data product of marine inorganic carbon chemistry parameters measured from seawater samples taken during biannual cruises between 2008 and 2017 in the northern Gulf of Alaska. Samples were collected each May and September over the 10 year period using a conductivity, temperature, depth (CTD) profiler coupled with a Niskin bottle rosette at stations including a long-term hydrographic survey transect known as the Gulf of Alaska (GAK) Line. This dataset includes discrete seawater measurements such as dissolved inorganic carbon and total alkalinity, which allows the calculation of other marine carbon parameters, including carbonate mineral saturation states, carbon dioxide (CO2), and pH. Cumulative daily Bakun upwelling indices illustrate the pattern of downwelling in the northern Gulf of Alaska, with a period of relaxation spanning between the May and September cruises. The observed time and space variability impart challenges for disentangling the OA signal despite this dataset spanning a decade. However, this data product greatly enhances our understanding of seasonal and interannual variability in the marine inorganic carbon system parameters. The product can also aid in the ground truthing of biogeochemical models, refining estimates of sea–air CO2 exchange, and determining appropriate CO2 parameter ranges for experiments targeting potentially vulnerable species. Data are available at https://doi.org/10.25921/x9sg-9b08 (Monacci et al., 2023).

Calcification and trophic responses of mesophotic reefs to carbonate chemistry variability

Mesophotic coral ecosystems (MCEs) are extensions of adjacent shallow water coral reefs. Accessibility to these ecosystems is challenging due to their depth limits (~ 30 – 150 m) and as a result, scientific knowledge of these reef systems is limited. It has been posited that the depth limits of MCEs diminish anthropogenic effects experienced by shallow reef systems. A lack of empirical measurements to date has made this hypothesis impossible to determine for mesophotic reef metabolism. The alkalinity anomaly technique was utilized to determine rates of net ecosystem calcification (NEC) and net ecosystem production (NEP) from 30, 40 and 60 m mesophotic reefs during a 15-month period. Seawater chemistry was determined to be chemically conducive for calcification (average aragonite saturation Ωaragonite of 3.58, average calcite saturation Ωcalcite of 5.44) with estimates of NEC indicating these reef systems were net accretive and within global average values for shallow coral reefs (&amp;lt; 30 m). The strongest periods of calcification occurred in late summer and were coupled with strong autotrophic signals. These episodes were followed by suppressed calcification and autotrophy and in the case of the 60 m reefs, a switch to heterotrophy. Whilst there was variability between the three reefs depths, the overall status of the mesophotic system was net autotrophic. This determination was the opposite of trophic status estimates previously described for adjacent shallow reefs. Whilst there were periods of net dissolution, the mesophotic reef system was net accretive (i.e., gross calcification &amp;gt; gross CaCO3 dissolution). The measured inorganic carbon chemistry and estimates of NEC and NEP represent the first such biogeochemical measurements for MCEs. The values established by this study demonstrate just how close these understudied ecosystems are in terms of the known boundary thresholds for low saturation state reefs. Making predictions on how these ecosystems will respond to future climatic conditions, will require greater sampling effort over long times scales to decouple the environmental controls exerted on such ecosystems.

GLODAPv2.2022: the latest version of the global interior ocean biogeochemical data product

Abstract. The Global Ocean Data Analysis Project (GLODAP) is a synthesis effort providing regular compilations of surface-to-bottom ocean biogeochemical bottle data, with an emphasis on seawater inorganic carbon chemistry and related variables determined through chemical analysis of seawater samples. GLODAPv2.2022 is an update of the previous version, GLODAPv2.2021 (Lauvset et al., 2021). The major changes are as follows: data from 96 new cruises were added, data coverage was extended until 2021, and for the first time we performed secondary quality control on all sulfur hexafluoride (SF6) data. In addition, a number of changes were made to data included in GLODAPv2.2021. These changes affect specifically the SF6 data, which are now subjected to secondary quality control, and carbon data measured on board the RV Knorr in the Indian Ocean in 1994–1995 which are now adjusted using certified reference material (CRM) measurements made at the time. GLODAPv2.2022 includes measurements from almost 1.4 million water samples from the global oceans collected on 1085 cruises. The data for the now 13 GLODAP core variables (salinity, oxygen, nitrate, silicate, phosphate, dissolved inorganic carbon, total alkalinity, pH, chlorofluorocarbon-11 (CFC-11), CFC-12, CFC-113, CCl4, and SF6) have undergone extensive quality control with a focus on systematic evaluation of bias. The data are available in two formats: (i) as submitted by the data originator but converted to World Ocean Circulation Experiment (WOCE) exchange format and (ii) as a merged data product with adjustments applied to minimize bias. For the present annual update, adjustments for the 96 new cruises were derived by comparing those data with the data from the 989 quality-controlled cruises in the GLODAPv2.2021 data product using crossover analysis. SF6 data from all cruises were evaluated by comparison with CFC-12 data measured on the same cruises. For nutrients and ocean carbon dioxide (CO2) chemistry comparisons to estimates based on empirical algorithms provided additional context for adjustment decisions. The adjustments that we applied are intended to remove potential biases from errors related to measurement, calibration, and data handling practices without removing known or likely time trends or variations in the variables evaluated. The compiled and adjusted data product is believed to be consistent to better than 0.005 in salinity, 1 % in oxygen, 2 % in nitrate, 2 % in silicate, 2 % in phosphate, 4 µmol kg−1 in dissolved inorganic carbon, 4 µmol kg−1 in total alkalinity, 0.01–0.02 in pH (depending on region), and 5 % in the halogenated transient tracers. The other variables included in the compilation, such as isotopic tracers and discrete CO2 fugacity (fCO2), were not subjected to bias comparison or adjustments. The original data, their documentation, and DOI codes are available at the Ocean Carbon and Acidification Data System of NOAA NCEI (https://www.ncei.noaa.gov/access/ocean-carbon-acidification-data-system/oceans/GLODAPv2_2022/, last access: 15 August 2022). This site also provides access to the merged data product, which is provided as a single global file and as four regional ones – the Arctic, Atlantic, Indian, and Pacific oceans – under https://doi.org/10.25921/1f4w-0t92 (Lauvset et al., 2022). These bias-adjusted product files also include significant ancillary and approximated data, which were obtained by interpolation of, or calculation from, measured data. This living data update documents the GLODAPv2.2022 methods and provides a broad overview of the secondary quality control procedures and results.

Effects of seawater pCO2 on the skeletal morphology of massive Porites spp. corals

Ocean acidification alters the dissolved inorganic carbon chemistry of seawater and can reduce the calcification rates of tropical corals. Here we explore the effect of altering seawater pCO2 on the skeletal morphology of 4 genotypes of massive Porites spp. which display widely different calcification rates. Increasing seawater pCO2 causes significant changes in in the skeletal morphology of all Porites spp. studied regardless of whether or not calcification was significantly affected by seawater pCO2. Both the median calyx size and the proportion of skeletal surface occupied by the calices decreased significantly at 750 µatm compared to 400 µatm indicating that polyp size shrinks in this genus in response to ocean acidification. The coenosteum, connecting calices, expands to occupy a larger proportion of the coral surface to compensate for this decrease in calyx area. At high seawater pCO2 the spines deposited at the skeletal surface became more numerous and the trabeculae (vertical skeletal pillars) became significantly thinner in 2 of the 4 genotypes. The effect of high seawater pCO2 is most pronounced in the fastest growing coral and the regular placement of trabeculae and synapticulae is disturbed in this genotype resulting in a skeleton that is more randomly organised. The study demonstrates that ocean acidification decreases the polyp size and fundamentally alters the architecture of the skeleton in this major reef building species from the Indo-Pacific Ocean.

Exploring Dissolved Organic Carbon Variations in a High Elevation Tropical Peatland Ecosystem: Cerro de la Muerte, Costa Rica

Tropical peatlands are distributed mainly in coastal lowlands; however high elevation regions exhibit a large prevalence of small and fragmented peatlands that are mostly understudied. Artificial drainage of peatlands to expand the area of cattle farming, horticulture, and urbanization is increasing carbon losses to the atmosphere and streams worldwide. Here, we present an exploratory characterization of dissolved carbon optical properties in ombrotrophic peat bogs of the Talamanca range of Costa Rica, across an altitudinal gradient (2,400–3,100 m a.s.l.) during the rainy season. Dissolved organic matter (DOM) sources and decomposition processes were evaluated in the light of dissolved organic and inorganic carbon (DOC and DIC), optical properties, and major water chemistry. DOC concentrations ranged from 0.2 up to 47.0 mg/L. DIC concentrations were below 2 mg/L and δ13CDIC values indicated a mixture between soil organic matter, CO2 in soil water, and to a lesser degree DIC derived from bacterial CO2. Absolute fluorescence intensity of humic-like peaks was 6–7 times greater than fresh-like peaks across all sites. Fluorescence peak ratios coupled with the biological and humification indexes point to a greater relative contribution of recalcitrant soil-derived DOM. Excitation/Emission matrices denoted a high prevalence of humic and fulvic acids in the peat bogs, with moderate intensities in soluble microbial by-products-like and aromatic protein regions at three sites. Our data provides a baseline to underpin tropical carbon dynamics across high elevation peatlands.

An updated version of the global interior ocean biogeochemical data product, GLODAPv2.2021

Abstract. The Global Ocean Data Analysis Project (GLODAP) is a synthesis effort providing regular compilations of surface-to-bottom ocean biogeochemical bottle data, with an emphasis on seawater inorganic carbon chemistry and related variables determined through chemical analysis of seawater samples. GLODAPv2.2021 is an update of the previous version, GLODAPv2.2020 (Olsen et al., 2020). The major changes are as follows: data from 43 new cruises were added, data coverage was extended until 2020, all data with missing temperatures were removed, and a digital object identifier (DOI) was included for each cruise in the product files. In addition, a number of minor corrections to GLODAPv2.2020 data were performed. GLODAPv2.2021 includes measurements from more than 1.3 million water samples from the global oceans collected on 989 cruises. The data for the 12 GLODAP core variables (salinity, oxygen, nitrate, silicate, phosphate, dissolved inorganic carbon, total alkalinity, pH, CFC-11, CFC-12, CFC-113, and CCl4) have undergone extensive quality control with a focus on systematic evaluation of bias. The data are available in two formats: (i) as submitted by the data originator but updated to World Ocean Circulation Experiment (WOCE) exchange format and (ii) as a merged data product with adjustments applied to minimize bias. For this annual update, adjustments for the 43 new cruises were derived by comparing those data with the data from the 946 quality controlled cruises in the GLODAPv2.2020 data product using crossover analysis. Comparisons to estimates of nutrients and ocean CO2 chemistry based on empirical algorithms provided additional context for adjustment decisions in this version. The adjustments are intended to remove potential biases from errors related to measurement, calibration, and data handling practices without removing known or likely time trends or variations in the variables evaluated. The compiled and adjusted data product is believed to be consistent with to better than 0.005 in salinity, 1 % in oxygen, 2 % in nitrate, 2 % in silicate, 2 % in phosphate, 4 µmol kg−1 in dissolved inorganic carbon, 4 µmol kg−1 in total alkalinity, 0.01–0.02 in pH (depending on region), and 5 % in the halogenated transient tracers. The other variables included in the compilation, such as isotopic tracers and discrete CO2 fugacity (fCO2), were not subjected to bias comparison or adjustments. The original data, their documentation, and DOI codes are available at the Ocean Carbon Data System of NOAA NCEI (https://www.ncei.noaa.gov/access/ocean-carbon-data-system/oceans/GLODAPv2_2021/, last access: 7 July 2021). This site also provides access to the merged data product, which is provided as a single global file and as four regional ones – the Arctic, Atlantic, Indian, and Pacific oceans – under https://doi.org/10.25921/ttgq-n825 (Lauvset et al., 2021). These bias-adjusted product files also include significant ancillary and approximated data and can be accessed via https://www.glodap.info (last access: 29 June 2021). These were obtained by interpolation of, or calculation from, measured data. This living data update documents the GLODAPv2.2021 methods and provides a broad overview of the secondary quality control procedures and results.

Atmospheric deposition of inorganic nutrients to the Western North Pacific Ocean

We evaluated the potential impacts of atmospheric deposition on marine productivity and inorganic carbon chemistry in the northwestern Pacific Ocean (8–39°N, 125–157°E). The nutrient concentration in atmospheric total suspended particles decreased exponentially with increasing distance from the closest land-mass (Asia), clearly revealing anthropogenic and terrestrial contributions. The predicted mean depositional fluxes of inorganic nitrogen were approximately 34 and 15 μmol m−2 d−1 to the west and east of 140°E, respectively, which were at least two orders of magnitude greater than the inorganic phosphorus flux. On average, atmospheric particulate deposition would support 3–4% of the net primary production along the surveyed tracks, which is equivalent to ~2% of the dissolved carbon increment caused by the penetration of anthropogenic CO2. Our observations generally fell within the ranges observed over the past 18 years, despite an increasing trend of atmospheric pollution in the source regions during the same period, which implies high temporal and spatial variabilities of atmospheric nutrient concentration in the study area. Continued atmospheric anthropogenic nitrogen deposition may alter the relative abundances of nitrogen and phosphorus.

Groundwater residence time estimates obscured by anthropogenic carbonate.

Groundwater is an important source of drinking and irrigation water. Dating groundwater informs its vulnerability to contamination and aids in calibrating flow models. Here, we report measurements of multiple age tracers (14C, 3H, 39Ar, and 85Kr) and parameters relevant to dissolved inorganic carbon (DIC) from 17 wells in California's San Joaquin Valley (SJV), an agricultural region that is heavily reliant on groundwater. We find evidence for a major mid-20th century shift in groundwater DIC input from mostly closed- to mostly open-system carbonate dissolution, which we suggest is driven by input of anthropogenic carbonate soil amendments. Crucially, enhanced open-system dissolution, in which DIC equilibrates with soil CO2, fundamentally affects the initial 14C activity of recently recharged groundwater. Conventional 14C dating of deeper SJV groundwater, assuming an open system, substantially overestimates residence time and thereby underestimates susceptibility to modern contamination. Because carbonate soil amendments are ubiquitous, other groundwater-reliant agricultural regions may be similarly affected.

A regional hindcast model simulating ecosystem dynamics, inorganic carbon chemistry, and ocean acidification in the Gulf of Alaska

Abstract. The coastal ecosystem of the Gulf of Alaska (GOA) is especially vulnerable to the effects of ocean acidification and climate change. Detection of these long-term trends requires a good understanding of the system’s natural state. The GOA is a highly dynamic system that exhibits large inorganic carbon variability on subseasonal to interannual timescales. This variability is poorly understood due to the lack of observations in this expansive and remote region. We developed a new model setup for the GOA that couples the three-dimensional Regional Oceanic Model System (ROMS) and the Carbon, Ocean Biogeochemistry and Lower Trophic (COBALT) ecosystem model. To improve our conceptual understanding of the system, we conducted a hindcast simulation from 1980 to 2013. The model was explicitly forced with temporally and spatially varying coastal freshwater discharges from a high-resolution terrestrial hydrological model, thereby affecting salinity, alkalinity, dissolved inorganic carbon, and nutrient concentrations. This represents a substantial improvement over previous GOA modeling attempts. Here, we evaluate the model on seasonal to interannual timescales using the best available inorganic carbon observations. The model was particularly successful in reproducing observed aragonite oversaturation and undersaturation of near-bottom water in May and September, respectively. The largest deficiency in the model is its inability to adequately simulate springtime surface inorganic carbon chemistry, as it overestimates surface dissolved inorganic carbon, which translates into an underestimation of the surface aragonite saturation state at this time. We also use the model to describe the seasonal cycle and drivers of inorganic carbon parameters along the Seward Line transect in under-sampled months. Model output suggests that the majority of the near-bottom water along the Seward Line is seasonally undersaturated with respect to aragonite between June and January, as a result of upwelling and remineralization. Such an extensive period of reoccurring aragonite undersaturation may be harmful to ocean acidification-sensitive organisms. Furthermore, the influence of freshwater not only decreases the aragonite saturation state in coastal surface waters in summer and fall, but it simultaneously decreases the surface partial pressure of carbon dioxide (pCO2), thereby decoupling the aragonite saturation state from pCO2. The full seasonal cycle and geographic extent of the GOA region is under-sampled, and our model results give new and important insights for months of the year and areas that lack in situ inorganic carbon observations.

PH affects growth, physiology and agar properties of agarophyte Gracilaria changii (Rhodophyta) under low light intensity from Morib, Malaysia

Changes in coastal water pH alter inorganic carbon chemistry and impose abiotic stress on photosynthetic marine organisms. The red algal cell wall contains sulfated agar which protects them against environmental stresses. In this study, we investigated the effects of three different pHs (6.61, 8.04 and 9.30) on Gracilaria changii cultured in artificial seawater for 3 and 6 days, respectively. The growth rate of G. changii was the highest and the lowest at pH 6.61 and pH 9.30, respectively. Partial thallus degradation was observed in seaweeds treated at pH 9.30. Upon a 3-day treatment, the levels of allophycocyanin, total phycobilins in G. changii cultured at pH 6.61, and all photosynthetic pigments in G. changii cultured at pH 9.30, were significantly lower than those cultured at pH 8.04. G. changii exposed to pH 9.30 for 6 days also had significantly lower levels of chlorophyll a and allophycocyanin than those treated at pH 8.04. A six-day treatment at pH 6.61 caused a decline in the content of chlorophyll a and carotenoids, but an increase in the levels of phycoerythrin, phycocyanin, and total phycobilins, compared to those treated at pH 8.04. G. changii samples treated at pH 6.61 and pH 9.30 have a higher agar content compared to those cultured at 8.04. Gel strength was significantly lower in seaweed cultured at pH 9.30, compared to those cultured at pH 8.04. Gelling temperature and 3,6-anhydrogalactose content of agar were significantly affected by different pHs, but no significant changes were found in the melting temperature, gel syneresis and sulfate content of agar upon treatments. These information enhance our knowledge on physiological response and agar production in G. changii at different pHs, and useful for optimization of seaweed cultivation system in future.

The combined effects of acidification and hypoxia on pH and aragonite saturation in the coastal waters of the California current ecosystem and the northern Gulf of Mexico

Inorganic carbon chemistry data from the surface and subsurface waters of the West Coast of North America have been compared with similar data from the northern Gulf of Mexico to demonstrate how future changes in CO2 emissions will affect chemical changes in coastal waters affected by respiration-induced hypoxia ([O2] ≤ ~ 60µmolkg−1). In surface waters, the percentage change in the carbon parameters due to increasing CO2 emissions are very similar for both regions even though the absolute decrease in aragonite saturation is much higher in the warmer waters of the Gulf of Mexico. However, in subsurface waters the changes are enhanced due to differences in the initial oxygen concentration and the changes in the buffer capacity (i.e., increasing Revelle Factor) with increasing respiration from the oxidation of organic matter, with the largest impacts on pH and CO2 partial pressure (pCO2) occurring in the colder West Coast waters. As anthropogenic CO2 concentrations begin to build up in subsurface waters, increased atmospheric CO2 will expose organisms to hypercapnic conditions (pCO2 >1000 µatm) within subsurface depths. Since the maintenance of the extracellular pH appears as the first line of defense against external stresses, many biological response studies have been focused on pCO2-induced hypercapnia. The extent of subsurface exposure will occur sooner and be more widespread in colder waters due to their capacity to hold more dissolved oxygen and the accompanying weaker acid-base buffer capacity. Under present conditions, organisms in the West Coast are exposed to hypercapnic conditions when oxygen concentrations are near 100µmolkg−1 but will experience hypercapnia at oxygen concentrations of 260µmolkg−1 by year 2100 under the highest elevated-CO2 conditions. Hypercapnia does not occur at present in the Gulf of Mexico but will occur at oxygen concentrations of 170µmolkg−1 by the end of the century under similar conditions. The aragonite saturation horizon is currently above the hypoxic zone in the West Coast. With increasing atmospheric CO2, it is expected to shoal up close to surface waters under the IPCC Representative Concentration Pathway (RCP) 8.5 in West Coast waters, while aragonite saturation state will exhibit steeper gradients in the Gulf of Mexico. This study demonstrates how different biological thresholds (e.g., hypoxia, CaCO3 undersaturation, hypercapnia) will vary asymmetrically because of local initial conditions that are affected differently with increasing atmospheric CO2. The direction of change in amplitude of hypercapnia will be similar in both ecosystems, exposing both biological communities from the West Coast and Gulf of Mexico to intensification of stressful conditions. However, the region of lower Revelle factors (i.e., the Gulf of Mexico), currently provides an adequate refuge habitat that might no longer be the case under the most severe RCP scenarios.

The fatty acid content of plankton is changing in subtropical coastal waters as a result of OA: Results from a mesocosm study

Ocean Acidification (OA) effects on marine plankton are most often considered in terms of inorganic carbon chemistry, but decreasing pH may influence other aspects of cellular metabolism. Here we present the effects of OA on the fatty acid (FA) content and composition of an artificial phytoplankton community (Phaeodactylum tricornutum, Thalassiosira weissflogii, and Emiliania huxleyi) in a fully replicated, ∼4 m3 mesocosm study in subtropical coastal waters (Wuyuan Bay, China, 24.52°N, 117.18°E) at present day (400 μatm) and elevated (1000 μatm) pCO2 concentrations. Phytoplankton growth occurred in three phases during the 33-day experiment: an initial exponential growth leading to senescence and a subsequent decline phase. Phytoplankton sampled from these mesocosms were fed to mesozooplankton collected by net haul from Wuyuan Bay. Concentrations of saturated fatty acids (SFA) in both phytoplankton and mesozooplankton remained high under acidified and non-acidified conditions. However, polyunsaturated fatty acids (PUFA) and monounsaturated fatty acids (MUFA) increased significantly more under elevated pCO2 during the late exponential phase (Day 13), indicating increased nutritional value for zooplankton and higher trophic levels. Indeed, uptake rates of the essential FA docosahexaenoic acid (C20:5n3, DHA) increased in mesozooplankton under acidified conditions. However, mesozooplankton grazing rates decreased overall with elevated pCO2. Our findings show that these selected phytoplankton species have a relatively high tolerance to acidification in terms of FA production, and local mesozooplankton in these subtropical coastal waters can maintain their FA composition under end of century ocean acidification conditions.

Reconstructing coral calcification fluid dissolved inorganic carbon chemistry from skeletal boron: An exploration of potential controls on coral aragonite B/Ca.

The boron geochemistry of coral skeletons reflects the dissolved inorganic carbon (DIC) chemistry of the calcification fluid from which the skeletons precipitates and may be a valuable tool to investigate the effects of climate change on coral calcification. In this paper I calculate the predicted B/Ca of aragonite precipitating from seawater based fluids as a function of pH, [DIC] and [Ca2+]. I consider how different co-precipitating DIC species affect aragonite B/Ca and also estimate the impact of variations in the B(OH)4−/co-precipitating DIC aragonite partition coefficient (KD), which may be associated with changes in the DIC and Ca2+ chemistry of the calcification fluid. The coral skeletal B/Ca versus calcification fluid pH relationships reported previously can be reproduced by estimating B(OH)4− and co-precipitating DIC speciation as a function of pHCF and assuming that KD are constant i.e. unaffected by calcification fluid saturation state. Assuming that B(OH)4− co-precipitates with CO32−, then observed patterns can be reproduced by a fluid with approximately constant [DIC] i.e. increasing pHCF concentrates CO32−, as a function of DIC speciation. Assuming that B(OH)4− co-precipitates with HCO3− only or CO32− + HCO3− then the observed patterns can be reproduced if [DIC]CF and pHCF are positively related i.e. if DIC is increasingly concentrated in the calcification fluid at higher pHCF probably by CO2 diffusion into the calcification site.

Carbonate system properties in the Gerlache Strait, Northern Antarctic Peninsula (February 2015): I. Sea–Air CO2 fluxes

Hydrographic and carbonate system properties were determined in the Gerlache Strait—a coastal site in the Northern Antarctic Peninsula (NAP)—during early February 2015. It was part of an effort to monitor changes in marine inorganic carbon chemistry in Antarctic coastal zones. Here we describe surface observations performed during the NAUTILUS I cruise and compare results with earlier studies in the region. The focus of this first part of this study is to describe the spatial patterns of sea–air carbon dioxide (CO2) fluxes and relating the results with physical-chemical and biological parameters. In order to determine the CO2 fluxes, we use several available parameterizations for estimation of the gas transfer velocity coefficient, thus providing a range of the results’ uncertainties. Contrasting with results found twenty years ago, the Gerlache Strait was estimated here to be a monthly net source for CO2 of 0.50±0.45molm−2 month−1 during February 2015, based on shipboard wind measurements and Wanninkhof's (2014) gas transfer velocity relationship. That was probably driven by to warm water intrusions in combination with a phytoplankton community mainly dominated by small flagellates (particularly cryptophytes). Yet, in order to determine whether the region acts as an annual sink or source of CO2, there is a need for additional studies focusing on short time-scales throughout a year.

Twenty Years of Marine Carbon Cycle Observations at Devils Hole Bermuda Provide Insights into Seasonal Hypoxia, Coral Reef Calcification, and Ocean Acidification

Open–ocean observations have revealed gradual changes in seawater carbon dioxide (CO2) chemistry resulting from uptake of atmospheric CO2 and ocean acidification (OA), but, with few long–term records (>five years) of the coastal ocean that can reveal the pace and direction of environmental change. In this paper, observations collected from 1996 to 2016 at Harrington Sound, Bermuda, constitute one of the longest time–series of coastal ocean inorganic carbon chemistry. Uniquely, such changes can be placed into the context of contemporaneous offshore changes observed at the nearby Bermuda Atlantic Time-series Study (BATS) site. Onshore, surface dissolved inorganic carbon (DIC) and partial pressure of CO2 (pCO2; >10% change per decade) have increased and OA indicators such as pH and calcium carbonate (CaCO3) saturation state (Ω) decreased from 1996–2016 at a rate of two to three times that observed offshore at BATS. Such changes, combined with reduction of total alkalinity over time, reveal a complex interplay of biogeochemical processes influencing Bermuda reef metabolism, including net ecosystem production (NEP=gross primary production–autotrophic and heterotrophic respiration) and net ecosystem calcification (NEC=gross calcification–gross CaCO3 dissolution). These long–term data show ae seasonal shift between wintertime net heterotrophy and summertime net autotrophy for the entire Bermuda reef system. Over annual time-scales, the Bermuda reef system does not appear to be in trophic balance, but rather slightly net heterotrophic. In addition, the reef system is net accretive (i.e., gross calcification > gross CaCO3 dissolution), but there were occasional periods when the entire reef system appears to transiently shift to net dissolution. A previous five–year study of the Bermuda reef suggested that net calcification and net heterotrophy have both increased. Over the past twenty years, rates of net calcification and net heterotrophy determined for the Bermuda reef system have increased by ~30%, most likely due to increased coral nutrition occurring in concert with increased offshore productivity in the surrounding subtropical North Atlantic Ocean. Importantly, this long–term study reveals that other environmental factors can mitigate against the effects of ocean acidification on coral reef calcification, at least over the past couple of decades.

Estimating Total Alkalinity in the Washington State Coastal Zone: Complexities and Surprising Utility for Ocean Acidification Research

Evidence of ocean acidification (OA) throughout the global ocean has galvanized some coastal communities to evaluate carbonate chemistry variations closer to home. An impediment to doing this effectively is that, often, only one carbonate system parameter is measured at a time, while two are required to fully constrain the inorganic carbon chemistry of seawater. In order to leverage the abundant single-carbonate-parameter datasets in Washington State for more rigorous OA research, we have characterized an empirical relationship between total alkalinity (TA) and salinity (TA = 47.7 × S + 647; 1σ = ±17 μmol kg−1) for regional surface waters (≤25 m) that is robust in the salinity range from 20 to 35 for all seasons. The relationship was evaluated using 5 years of 3-h contemporaneous observations of salinity, carbon dioxide partial pressure (pCO2), and pH from a surface mooring on the outer coast of Washington. In situ pCO2 observations and salinity-based estimates of TA were used to calculate pH for comparison with in situ pH measurements. On average, the calculated pH values were 0.02 units lower than the measured pH values across multiple pH sensor deployments and showed extremely high fidelity in tracking the measured high-frequency pH variations. Our results indicate that the TA-salinity relationship will be a useful tool for expanding single-carbonate-parameter datasets in Washington State and quality controlling dual pCO2-pH time series.

Dense water flow and carbonate system in the southern Adriatic: A focus on the 2012 event

The active deep overturning circulation of the Mediterranean is emerging as one of the most effective mechanisms in transporting the atmospheric imprint on the carbon cycle to the interior of the basin. There is growing evidence that sites of dense water formation over the continental shelf, such as the Northern Adriatic Sea, play a key role in this process. Nevertheless, little is known about the inorganic carbon chemistry of the Adriatic sea, and CO2 absorption and its fate.The winter of 2012 experienced peculiar meteorological conditions with an extended period of cold weather with strong winds that triggered, in February, a massive formation of an extremely cold and dense (potential density anomaly >30.00kgm−3) Northern Adriatic Dense Water (NAdDW) water mass. This event provided a unique opportunity to study this process at sub-basin scale taking into account CO2 adsorption within the NAdDW source area (the Gulf of Trieste in the northern Adriatic), and its spreading over the shelf and into the Southern Adriatic Pit.The northern Adriatic and the Gulf of Trieste, during winter, act as a CO2 sink. The average air-sea CO2 flux of 60mmolm−2 d−1 estimated during the exceptional 2012 event was at least 3 times higher than the flux measured in winter 2008 when dense water was produced through the same mechanism but under less extreme conditions. In winter 2012, absorbed CO2 resulted in the decrease of pHT25 down to 7.907 (− 0.034 pHT units) and the strong evaporation induced by wind-increased total alkalinity (TA) to 2673 (+ 16μmolkg−1).Following its formation in the North, the NAdDW plume entering the Southern Adriatic, observed in March 2012, exhibited significantly modified values. The plume was characterized by colder temperature (~ 10°C), lower pHT25 (7.947 pHT units) and higher alkalinity (2635μmolkg−1) than the surrounding water masses along the western Adriatic shelf. However, the signal of atmospheric CO2 enrichment was weaker than in the northern Adriatic source region, as well as positive apparent oxygen utilization (AOU) values (~ 20μmolkg−1) were recorded. This is suggestive of oxygen consumption in the water mass.Observed changes in both physical and biogeochemical properties were similar to those observed in 2008, suggesting that mixing with Levantine Intermediate Waters (LIW) was the main driver modulating the changes of AOU and inorganic carbon chemistry in both winters. The rising of pHT25 and AOU due to the mixing indicates that NAdDW, at its origin, was richer in atmospheric CO2 than the LIW was, thus confirming the relevance of the Northern Adriatic Sea for CO2 adsorption.The study provides the first characterization of inorganic carbon chemistry, including carbonate minerals saturation states (ΩAr and ΩCa), in the bottom waters both on the slope and along the expected pathways of dense water cascading in the Adriatic Sea. Therefore, it can represent a baseline to improve the knowledge on the acidification process and impacts as well as being useful for comparison with other benthic environments.