Seawater CO2 Research Articles

Seasonal marine carbon system processes in an Arctic coastal landfast sea ice environment observed with an innovative underwater sensor platform

Studying carbon dioxide in the ocean helps to understand how the ocean will be impacted by climate change and respond to increasing fossil fuel emissions. The marine carbonate system is not well characterized in the Arctic, where challenging logistics and extreme conditions limit observations of atmospheric CO2 flux and ocean acidification. Here, we present a high-resolution marine carbon system data set covering the complete cycle of sea-ice growth and melt in an Arctic estuary (Nunavut, Canada). This data set was collected through three consecutive yearlong deployments of sensors for pH and partial pressure of CO2 in seawater (pCO2sw) on a cabled underwater observatory. The sensors were remarkably stable compared to discrete samples: While corrections for offsets were required in some instances, we did not observe significant drift over the deployment periods. Our observations revealed a strong seasonality in this marine carbon system. Prior to sea-ice formation, air–sea gas exchange and respiration were the dominant processes, leading to increasing pCO2sw and reduced aragonite saturation state (ΩAr). During sea-ice growth, water column respiration and brine rejection (possibly enriched in dissolved inorganic carbon, relative to alkalinity, due to ikaite precipitation in sea ice) drove pCO2sw to supersaturation and lowered ΩAr to < 1. Shortly after polar sunrise, the ecosystem became net autotrophic, returning pCO2sw to undersaturation. The biological community responsible for this early switch to autotrophy (well before ice algae or phytoplankton blooms) requires further investigation. After sea-ice melt initiated, an under-ice phytoplankton bloom strongly reduced aqueous carbon (chlorophyll-a max of 2.4 µg L–1), returning ΩAr to > 1 after 4.5 months of undersaturation. Based on simple extrapolations of anthropogenic carbon inventories, we suspect that this seasonal undersaturation would not have occurred naturally. At ice breakup, the sensor platform recorded low pCO2sw (230 µatm), suggesting a strong CO2 sink during the open water season.

Surface CO2 system dynamics in the Gulf of Anadyr during the open water season

The Gulf of Anadyr (GA), one of the largest and most poorly investigated gulfs of the Bering Sea, is an important part of the Pacific Arctic. Drivers and mechanisms responsible for the spatial variations in surface seawater CO2 system parameters and associated air–sea CO2 fluxes were investigated during three oceanographic cruises conducted in the GA during the open water season of 1992, 2002, and 2011. It was shown that the surface waters of the GA were moderate to strong sinks for atmospheric CO2 during this season: mean air-sea CO2 fluxes for the investigated areas of the GA, for the three cruises, were −31, −15, and −30 mmol CO2 m−2 d−1, respectively. The summer air-sea CO2 flux was attributed to intensive phytoplankton bloom, and fall CO2 uptake coincided with a period of strong winds and seasonal enhanced primary production. The surface waters of the GA were supersaturated with respect to aragonite during the investigated period. Anadyr Strait, a region of high hydrodynamic activity, was the only area where CO2 efflux was observed. Surface waters of the strait were supersaturated with respect to CO2 and in quasi-equilibrium with respect to aragonite. We found that during the late summer/fall season, the Anadyr Current exported a well-mixed, relatively cold, salty, nutrient- and CO2-rich water through the western Anadyr Strait into the Chirikov Basin. Our research highlights the need for mesoscale studies of the western Bering Sea to produce the most accurate assessment of the regional CO2 budget.

Volcanic CO2 seep geochemistry and use in understanding ocean acidification

Ocean acidification is one of the most dramatic effects of the massive atmospheric release of anthropogenic carbon dioxide (CO2) that has occurred since the Industrial Revolution, although its effects on marine ecosystems are not well understood. Submarine volcanic hydrothermal fields have geochemical conditions that provide opportunities to characterise the effects of elevated levels of seawater CO2 on marine life in the field. Here, we review the geochemical aspects of shallow marine CO2-rich seeps worldwide, focusing on both gas composition and water chemistry. We then describe the geochemical effects of volcanic CO2 seepage on the overlying seawater column. We also present new geochemical data and the first synthesis of marine biological community changes from one of the best-studied marine CO2 seep sites in the world (off Vulcano Island, Sicily). In areas of intense bubbling, extremely high levels of pCO2 (> 10,000 μatm) result in low seawater pH (< 6) and undersaturation of aragonite and calcite in an area devoid of calcified organisms such as shelled molluscs and hard corals. Around 100–400 m away from the Vulcano seeps the geochemistry of the seawater becomes analogous to future ocean acidification conditions with dissolved carbon dioxide levels falling from 900 to 420 μatm as seawater pH rises from 7.6 to 8.0. Calcified species such as coralline algae and sea urchins fare increasingly well as sessile communities shift from domination by a few resilient species (such as uncalcified algae and polychaetes) to a diverse and complex community (including abundant calcified algae and sea urchins) as the seawater returns to ambient levels of CO2. Laboratory advances in our understanding of species sensitivity to high CO2 and low pH seawater, reveal how marine organisms react to simulated ocean acidification conditions (e.g., using energetic trade-offs for calcification, reproduction, growth and survival). Research at volcanic marine seeps, such as those off Vulcano, highlight consistent ecosystem responses to rising levels of seawater CO2, with the simplification of food webs, losses in functional diversity and reduced provisioning of goods and services for humans.

Process improvement of sea water reverse osmosis (SWRO) and subsequent decarbonization

An enhanced RO desalination system is presented which improves the efficiency of the coagulation system and helps to maintain (or even increase) first-pass recovery ratios, while simultaneously reducing the need for industrial acids, and antiscalants in the second-pass that potentially cause biofouling. The aim is to eliminate the use of expensive industrial acids for acidification of seawater during RO pretreatment processes; instead carbon dioxide (CO2) is injected after capturing it from the exhaust of power plants. The injection of CO2 into seawater essentially reduces the carbon footprint of the RO process. CO2 addition reduces scaling potential of carbonates and allows a higher recovery operation, it will also make acid and antiscalant dosing obsolete. The dissolved CO2 in seawater passes through the RO membranes. Consequently, the CO2 addition also lowers the pH of the RO permeate and brine, the presence of additional CO2 in RO permeate reduces the need of food grade CO2 in the post-treatment process. Low pH brine stream is an ideal condition for further brine concentration processes. Based on the cost of the carbon capture technology, a Life-Cycle Cost Analysis (LCCA) has been performed to access different alternatives for seawater acidification and determine the most cost-effective option.

Effects of warming and CO2 enrichment on O2 consumption, porewater oxygenation and pH of subtidal silt sediment

We investigated the effects of seawater warming and CO2 enrichment on the microbial community metabolism (using O2 consumption as a proxy) in subtidal silt sediment. Intact sediment cores, without large dwelling infauna, were incubated for 24 days at 12 (in situ) and 18 °C to confirm the expected temperature response. We then enriched the seawater overlying a subset of cold and warm-incubated cores with CO2 (+ ΔpCO2: 253–396 µatm) for 16 days and measured the metabolic response. Warming increased the depth-integrated volume-specific O2 consumption (Rvol), the maximum in the volume-specific O2 consumption at the bottom of the oxic zone (Rvol,bmax) and the volume-specific net O2 production (Pn,vol), and decreased the O2 penetration depth (O2-pd) and the depth of Rvol,bmax (depthbmax). Benthic photosynthesis oscillated the pH in the upper 2 mm of the sediment. CO2 enrichment of the warm seawater did not alter this oscillation but shifted the pH profile towards acidity; the effect was greatest at the surface and decreased to a depth of 12 mm. Confoundment rendered the CO2 treatment of the cold seawater inconclusive. In warm seawater, we found no statistically clear effect of CO2 enrichment on Rvol, Rvol,bmax, Pn,vol, O2-pd, or depthbmax and therefore suspect that this perturbation did not alter the microbial community metabolism. This confirms the conclusion from experiments with other, contrasting types of sediment.

Progressive seawater acidification on the Great Barrier Reef continental shelf

Coral reefs are highly sensitive to ocean acidification due to rising atmospheric CO2 concentrations. We present 10 years of data (2009–2019) on the long-term trends and sources of variation in the carbon chemistry from two fixed stations in the Australian Great Barrier Reef. Data from the subtropical mid-shelf GBRWIS comprised 3-h instrument records, and those from the tropical coastal NRSYON were monthly seawater samples. Both stations recorded significant variation in seawater CO2 fugacity (fCO2), attributable to seasonal, daytime, temperature and salinity fluctuations. Superimposed over this variation, fCO2 progressively increased by > 2.0 ± 0.3 µatm year−1 at both stations. Seawater temperature and salinity also increased throughout the decade, whereas seawater pH and the saturation state of aragonite declined. The decadal upward fCO2 trend remained significant in temperature- and salinity-normalised data. Indeed, annual fCO2 minima are now higher than estimated fCO2 maxima in the early 1960s, with mean fCO2 now ~ 28% higher than 60 years ago. Our data indicate that carbonate dissolution from the seafloor is currently unable to buffer the Great Barrier Reef against ocean acidification. This is of great concern for the thousands of coral reefs and other diverse marine ecosystems located in this vast continental shelf system.

AIR-SEA FLUX OF CO2 IN THE WATERS OF KARIMUNJAWA ISLAND, INDONESIA

The purpose of this study was to determine the distribution of CO2 flux in Karimunjawa in the east monsoon. The variables in this study were temperature; pH; salinity; DO; CO2 atm was measured using a CO2 meter; chlorophyll-a, phosphate, silicate were measured spectrophotometric method. Total Alkalinity / TA was measured using the titration method with the principle of changing pH; DIC (Dissolved Inorganic Carbon) was measured using CO2sys software. The partial pressure of seawater carbon dioxide calculated using formula: pCO2sea = 6.31T2 + 61,9 Chla2 – 365.85T – 94.41 Chl-a +5715.94, the partial pressure of atmospheric carbon dioxide calculated using formula: pCO2atm = xCO2atm (pb - pH2O). The calculation of the estimated CO2 flux using the formula: Flux CO2 = Kh x kwa x (∆pCO2) , if the CO2 flux has a positive value water acts as a CO2 source, and if it is negative, the waters act as a CO2 sink.. CO2 flux in Karimunjawa waters during east monsoon (represented by August 2018) showed that in Karimunjawa waters with normal pH 7.2-7.4 were dominated by bicarbonate ion HCO3-with an average value of DIC 1847.24 µmol/kg dan TA 1912.51 µmol/kg. The partial pressure of seawater CO2 is higher than the partial pressure of atmospheric CO2 this indicates that the role of Karimunjawa waters as a source of CO2 where there is release of carbon dioxide into the atmosphere with CO2 flux values ranging from 8.549 – 13.272 mmol m-2 day-1. The variables that affect the flux of CO2 were the pCO2sea and ΔpCO2 with a very strong and positive correlation. These two variables were influenced by sea water temperature, salinity, chlorophyll-a, phosphate and silicate.

The Impacts of Ocean Acidification on Marine Ecosystems and Reliant Human Communities

Rising atmospheric carbon dioxide (CO2) levels, from fossil fuel combustion and deforestation, along with agriculture and land-use practices are causing wholesale increases in seawater CO2 and inorganic carbon levels; reductions in pH; and alterations in acid-base chemistry of estuarine, coastal, and surface open-ocean waters. On the basis of laboratory experiments and field studies of naturally elevated CO2 marine environments, widespread biological impacts of human-driven ocean acidification have been posited, ranging from changes in organism physiology and population dynamics to altered communities and ecosystems. Acidification, in conjunction with other climate change–related environmental stresses, particularly under future climate change and further elevated atmospheric CO2 levels, potentially puts at risk many of the valuable ecosystem services that the ocean provides to society, such as fisheries, aquaculture, and shoreline protection. Thisreview emphasizes both current scientific understanding and knowledge gaps, highlighting directions for future research and recognizing the information needs of policymakers and stakeholders.

Comparison and suggestion of indicators of concentrations associated with CO2 in seawater considering biological activity

Carbon dioxide capture and storage is expected to reduce large amount of CO2 emissions from pointwise large sources, such as coal power plants, by 2030 in Japan. For offshore CO2 storage, it is necessary to monitor concentrations associated with CO2 in seawater to ensure safe storage. To do so, it is also necessary to know the baseline concentrations in the target seas. However, such concentrations have large regional and seasonal variations, mainly because of biological activity. In this study, we compared various indicators of CO2 dissolved in seawater, using the seawater off Tomakomai, Japan, observed between 2013 and 2018. Among the indicators, we found very strong correlations between [nDIC + kDO] and T and between [DIC − 0.5TA + kDO] and T. These indicators are thought to be effective for investigating the possibility of unexpected leakage of CO2 stored in sub-seabed geological formations. However, data always contain a degree of scattering, even when their correlation is very high. In the case of the seawater off Tomakomai, the data that exceeded a criteria based on the residual standard deviation of some indicators were not necessarily the same as those of the other indicators. Therefore, it is suggested that two or more, different types of indicators should be used, such as pCO2-[DO saturation] and [nDIC + kDO]-T or [DIC − 0.5TA + kDO]-T.

Ervilia castanea (Mollusca, Bivalvia) populations adversely affected at CO2 seeps in the North Atlantic

Sites with naturally high CO2 conditions provide unique opportunities to forecast the vulnerability of coastal ecosystems to ocean acidification, by studying the biological responses and potential adaptations to this increased environmental variability. In this study, we investigated the bivalve Ervilia castanea in coastal sandy sediments at reference sites and at volcanic CO2 seeps off the Azores, where the pH of bottom waters ranged from average oceanic levels of 8.2, along gradients, down to 6.81, in carbonated seawater at the seeps. The bivalve population structure changed markedly at the seeps. Large individuals became less abundant as seawater CO2 levels rose and were completely absent from the most acidified sites. In contrast, small bivalves were most abundant at the CO2 seeps. We propose that larvae can settle and initially live in high abundances under elevated CO2 levels, but that high rates of post-settlement dispersal and/or mortality occur. Ervilia castanea were susceptible to elevated CO2 levels and these effects were consistently associated with lower food supplies. This raises concerns about the effects of ocean acidification on the brood stock of this species and other bivalve molluscs with similar life history traits.

The spatiotemporal variation and control mechanism of surface pCO2 in winter in Jiaozhou Bay, China

In many mid-latitude coastal waters during winter months, in addition to temperature, the large change in biogeochemical processes often influence and complicate the surface partial pressure of CO2 (pCO2). Based on the hydrological and carbonate parameters in seven cruises, this study analysed the evolution process and explored the control mechanism of the surface pCO2 in Jiaozhou Bay, China, from December to March. The results showed that the pCO2 ranged from 157 μatm to 647 μatm, and the bay represented a sink for atmospheric CO2 (−4.02 mmol m−2 d−1) in the whole winter. The non-temperature processes were the dominant factors affecting intra-winter pCO2 variation. In December, the bay was dominated by aerobic respiration and acted as a CO2 source (1.61 mmol m−2 d−1). From early January to late February, however, the vigorous growth of cold algae caused strong primary production, and the bay presented as a CO2 sink (from −3.68 mmol m−2 d−1 in early January to −10.82 mmol m−2 d−1 in late February). In March, primary production weakened and the effects of the CaCO3 precipitation appeared, and the strength of the CO2 sink was obviously weakened (−1.72 mmol m−2 d−1). Meanwhile, the water temperature decreased gradually from December to late January and then increased until March, and it further expanded the variation range of pCO2. Our results highlight the obvious source/sink change in mid-latitude seawater CO2 in winter, while more field observations are still needed to further understand the complicated biogeochemical processes and its influence on seawater pCO2.

Progress in thermodynamic analyses and optimizations for key component units in sea-based fuel synthesis systems

This paper provides a brief introduction to the finite-time thermodynamic studies performed for chemical reaction processes. The research progress in the thermodynamic analyses and optimizations of the key component units in the two subsystems of the sea-based fuel synthesis system are described. This paper describes the component units in the carbon- and hydrogen-capture subsystems (i.e., the modules on the electrochemical acidification of seawater, extraction of CO2 in the acidic seawater, and production of hydrogen). This paper also describes the component units in the catalytic synthesis subsystems, which include the reverse water gas shift unit reactor and the Fischer-Tropsch synthesis unit reactor in the fuel synthesis technological pathway of long-chain hydrocarbon cracking; the subsystem also includes the CO2 hydrogenation of light olefins unit reactor and the olefins oligomerization unit reactor in the fuel synthesis technological pathway of short-chain hydrocarbon polymerization. Modeling and performance optimizations were performed, and the thermal design and optimization for the key component units of the sea-based fuel synthesis system were explored by combining the thermodynamics, heat transfer, fluid dynamics, chemical reaction kinetics, optimal control theory, and multiple-objective optimization methods. From shallow to deep, a one-dimensional plug-flow reactor model (with a completely temperature-controlled heat reservoir) and a two-dimensional pseudo-homogeneous reactor model (with a real heat reservoir) were established; high-temperature helium was employed as the heat carrier. From the reversible to irreversible models, the classical equilibrium thermodynamic model and finite-time thermodynamic model that considers various irreversible factors were established. From a single objective to multiple-objective optimizations, the optimizations were performed for single objectives, including the minimum entropy generation rate and minimum specific entropy generation rate (i.e., the entropy generation rate averaged by the production rate of target products), and multiple-objectives by comprehensively considering the production rate of the target products’ maximization and entropy generation rate minimization. The outlet mean conversion rate maximization and maximum radial temperature difference minimization were performed. Some results with important theoretical significances and application values were obtained, which can provide the scientific bases and theoretical guidelines for the design and optimization for the sea-based fuel synthesis systems. One of the important developmental trends was the constructal thermodynamic optimization for the two subsystems and the integration of the full sea-based fuel synthesis system with the component units.

A marine photosynthetic microbial cell factory as a platform for spider silk production

Photosynthetic microorganisms such as cyanobacteria, purple bacteria and microalgae have attracted great interest as promising platforms for economical and sustainable production of bioenergy, biochemicals, and biopolymers. Here, we demonstrate heterotrophic production of spider dragline silk proteins, major ampullate spidroins (MaSp), in a marine photosynthetic purple bacterium, Rhodovulum sulfidophilum, under both photoheterotrophic and photoautotrophic growth conditions. Spider silk is a biodegradable and biocompatible material with remarkable mechanical properties. R. sulfidophilum grow by utilizing abundant and renewable nonfood bioresources such as seawater, sunlight, and gaseous CO2 and N2, thus making this photosynthetic microbial cell factory a promising green and sustainable production platform for proteins and biopolymers, including spider silks.

CO2 Enrichment Stimulates Dissolved Organic Carbon Release in Coral Reef Macroalgae.

Dissolved organic carbon (DOC) released by macroalgae is important in the context of coral reef degradation as it contributes to coral mortality by promoting bacterial metabolism on the coral surface. Using experimental carbon dioxide (CO2 ) manipulations in outdoor flow-through tanks, we found that seawater CO2 enrichment enhances daily net DOC release in a range of macroalgal species in the Great Barrier Reef (Australia). There was, however, large variability in DOC release among species, light and dark conditions, and CO2 exposure times. Under light conditions, DOC release in the red macroalga Amansia was 15 times higher under high CO2 conditions compared to ambient CO2 , however, CO2 enhancement did not affect DOC production in the other species. Results from the night incubations were more consistent as three of the four species (Amansia, Lobophora, and Sargassum) enhanced DOC release when enriched with CO2 . DOC fluxes shifted from production in the 1-d incubations to consumption in the 19-d experiment under light conditions, suggesting an important role of bacteria in DOC balances. The results suggest that rising CO2 (and ocean acidification) will continue to intensify space competition in favor of the macroalgae, potentially exacerbating reef degradation and ecological phase shifts from coral to macroalgal dominance.

Midinfrared Sensor System Based on Tunable Laser Absorption Spectroscopy for Dissolved Carbon Dioxide Analysis in the South China Sea: System-Level Integration and Deployment.

System-level integration of a midinfrared carbon dioxide (CO2) sensor system based on tunable laser absorption spectroscopy (TLAS) was realized for the analysis of dissolved CO2 in seawater, employing an interband cascade laser (ICL) centered at 4319 nm and a multipass cell (MPC) with an optical path length of 29.8 m. At a low measurement pressure of 30 Torr, three absorption lines of 12CO2 were selected to realize different measurement ranges and a 13CO2 absorption line was targeted for simultaneous isotopic abundance analysis of δ13CO2. The sensor system was compactly integrated into a standalone system with automatic operation for underwater field deployment, and the working process was controlled by a specially designed electrical system. A gas-liquid separator system was developed for CO2 extraction from water, and a pressure-control mechanism with two operation modes (i.e., static and dynamic modes) was proposed to make the sensor system applicable under a deep-sea environment. A series of experiments were carried out in the laboratory for performance assessment of the developed sensor system employed for the analysis of dissolved CO2 in water. The sensor was deployed for a field test for natural gas hydrates exploration at an underwater depth of 0-2000 m in the South China Sea, with the sensor operating normally during the deployment.

Novel reverse radioisotope labelling experiment reveals carbon assimilation of marine calcifiers under ocean acidification conditions

Abstract Ocean acidification by anthropogenic carbon dioxide emissions is projected to depress metabolic and physiological activity in marine calcifiers. To evaluate the sensitivity of marine organisms against ocean acidification, the assimilation of nutrients into carbonate shells and soft tissues must be examined. We designed a novel experimental protocol, reverse radioisotope labelling, to trace partitioning of nutrients within a single bivalve species under ocean acidification conditions. Injecting CO2 gas, free from radiocarbon, can provide a large contrast between carbon dissolved in the water and the one assimilated from atmosphere. By culturing modern aquifer organisms in acidified seawater, we were able to determine differences in the relative contributions of the end members, dissolved inorganic carbon (DIC) in seawater and metabolic CO2, to shell carbonate and soft tissues. Under all pCO2 conditions (463, 653, 872, 1,137 and 1,337 μatm), radiocarbon (Δ14C) values of the bivalve Scapharca broughtonii shell were significantly correlated with seawater DIC values; therefore, shell carbonate was derived principally from seawater DIC. The Δ14C results together with stable carbon isotope (δ13C) data suggest that in S. broughtonii shell δ13C may reflect the kinetics of isotopic equilibration as well as end‐member contributions; thus, care must be taken when analysing end‐member contributions by a previous method using δ13C. The insensitivity of S. broughtonii to perturbations in pCO2 up to at least 1,337 µatm indicates that this species can withstand ocean acidification. Usage of radioisotope to dope for tracer experiments requires strict rules to conduct any operations. Yet, reverse radioisotope labelling proposing in this study has a large advantage and is a powerful tool to understanding physiology of aquifer organisms that can be applicable to various organisms and culture experiments, such as temperature, salinity and acidification experiments, to improve understanding of the proportions of nutrients taken in by marine organisms under changing environments.

Refining the alkenone-pCO2 method II: Towards resolving the physiological parameter ‘b’

Haptophyte algal biomarkers called alkenones are widely used to reconstruct atmospheric CO2 in Earth’s Cenozoic history. This method is based on the notion that the algal carbon isotope fractionation during photosynthesis, as represented by εp37:2, is a function of seawater CO2 concentration and algal physiology. Constraining the algal physiological parameter, known as the ‘b’ term, is the key for successful applications of the alkenone-CO2 method. Using sensitivity analyses, we show that the growth rate (μ), cell size (r), and membrane permeability (P) are the most important variables to determine b. For all life on Earth, body size is a key factor that regulates metabolic rates. Exploiting the interdependence between phytoplankton cell size and growth rate, and specifically, the r – μ relationship for coccolithophores, we show that the length of fossil coccoliths (Lcoccolith) produced by ancient alkenone-synthesizers can be used to estimate r and therefore μ. Combining our new Lcoccolith data and published εp37:2 from the South China Sea Site MD01-2392, existing results from ODP Site 925, and ice core CO2, we determined the cell membrane permeability (P = 5.09 × 10−5 m s−1) for the Pleistocene community employing a bootstrap resampling technique. These new methods of constraining r, μ and P, combined with proxy-derived temperature (T), led us to rebuild b as a variable for each sample individually, which is subsequently used for alkenone-CO2 calculations. Application of this approach established pCO2 of the last 3 glacial-interglacial cycles, which turns out to be comparable with the ice core data in both the amplitude of changes and absolute values. It also reconciles the published Eocene – Oligocene alkenone-CO2 data which showed large geographical differences, with the new estimates much more consistent among different sites, and in line with other proxy-based results and ice sheet model predictions.

Assessment of pH dependent errors in spectrophotometric pH measurements of seawater

A recent analysis of full water column hydrographic data revealed a pH-dependent discrepancy between spectrophotometrically measured pH using purified meta-cresol purple and pH calculated from dissolved inorganic carbon (DIC) and total alkalinity (TA). The discrepancy (pHspec – pHTA,DIC) is approximately −0.018 and 0.014 at pH 7.4 and 8.2, respectively. This discrepancy has a wide range of implications for marine inorganic carbon measurements, such as establishing robust calibration protocols for pH sensors operating on profiling floats. Here, we conducted a series of lab based experiments to assess the magnitude of pH-dependent errors for spectrophotometric pH measurements in seawater by directly comparing its performance to pH measured by an Ion Sensitive Field Effect Transistor (ISFET) pH sensor known to have Nernstian behavior. Natural seawater was titrated with high CO2 seawater while simultaneously measuring pH using spectrophotometry and an ISFET sensor over a large range in pH (7–8.5) and temperature (5–30 °C). The two pH measurements were consistent to better than ±0.003 (range) at all temperatures except at 5 and 10 °C and very low and high pH, where discrepancies were as large as ±0.005. These results demonstrate that pH-dependent errors in spectrophotometric pH measurements can be rejected as the cause of the pH-dependent discrepancy between pHspec and pHTA,DIC. The cause of this discrepancy is thus likely due to our incomplete understanding of the marine inorganic carbon model that could include errors in thermodynamic constants, concentrations of major ions in seawater, systematic biases in measurements of TA or DIC, or contributions of organic compounds that are not accounted for in the definition of total alkalinity. This should be a research priority for the inorganic carbon community.

Responses of Intertidal Bacterial Biofilm Communities to Increasing pCO2.

The effects of ocean acidification on ecosystems remain poorly understood, because it is difficult to simulate the effects of elevated CO2 on entire marine communities. Natural systems enriched in CO2 are being used to help understand the long-term effects of ocean acidification in situ. Here, we compared biofilm bacterial communities on intertidal cobbles/boulders and bedrock along a seawater CO2 gradient off Japan. Samples sequenced for 16S rRNA showed differences in bacterial communities with different pCO2 and between habitat types. In both habitats, bacterial diversity increased in the acidified conditions. Differences in pCO2 were associated with differences in the relative abundance of the dominant phyla. However, despite the differences in community composition, there was no indication that these changes would be significant for nutrient cycling and ecosystem function. As well as direct effects of seawater chemistry on the biofilm, increased microalgal growth and decreased grazing may contribute to the shift in bacterial composition at high CO2, as documented by other studies. Thus, the effects of changes in bacterial community composition due to globally increasing pCO2 levels require further investigation to assess the implications for marine ecosystem function. However, the apparent lack of functional shifts in biofilms along the pCO2 gradient is a reassuring indicator of stability of their ecosystem functions in shallow ocean margins.

Seasonal dynamics of seawater CO2 system at a coastal site near the southern tip of Izu Peninsula, Japan

To elucidate how variables of the seawater CO2 system in surface waters have been changing seasonally and the mechanisms responsible for these changes in the area off the south coast of central Honshu Island, Japan, we made time-series measurements of total dissolved inorganic carbon (DIC), total alkalinity (TA), inorganic macronutrient and chlorophyll a concentrations as well as temperature and salinity at a near-shore station off Shimoda city near the southern tip of the Izu Peninsula over 19 months from November 2011 to June 2013. The oceanographic setting in our study site is characterized by seasonal stratification, low salinity in summer, and well-mixed water column in winter. A large bloom of phytoplankton developed in spring, thereafter nutrients were depleted within the mixed layer in summer. DIC exhibited large seasonal variations and ranged from 1967 µmol kg−1 in summer to 2073 µmol kg−1 in winter when normalized to a salinity of 35, because of biological production in the spring and summer and vertical mixing in autumn and winter, as shown by multiple regression analysis in which variations of normalized DIC (nDIC) are estimated from variations in temperature (13.3–25.5 °C) and chlorophyll concentrations (0.27–3.9 μg l−1). We observed a decrease of TA due to dilution by precipitation and river runoff in summer and a trend of salinity-normalized TA increase over time. The saturation state of the calcium carbonate mineral aragonite Ωarg varied seasonally from 2.40 in winter to 3.58 in summer. The Ωarg in the present study was calculated using DIC, TA, temperature and salinity, and we applied sensitivity analysis for these parameters. Ωarg was predominantly controlled by the large variations of DIC. The combination of these results from the station off Shimoda and from an offshore station at 34° N, 137° E to the west allow us to predict Ωarg with high precision for temporal and spatial variations. It suggests that in winter, there is a meridional gradient of Ωarg in the region off the southern coast of central Honshu Island, with considerably lower Ωarg in the coastal zone.