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In this work, we present, for the first time, the seawater carbonate system measurements of two coastal time-series in the NW Mediterranean Sea, L'Estartit Oceanographic Station (EOS; 42.05°N 3.2542°E) and the Blanes Bay Microbial Observatory (BBMO; 41.665°N 2.805°E). At these two time-series, measurements of total alkalinity (TA), pH, and associated variables, such as dissolved inorganic nutrients, temperature, and salinity, have been performed monthly since 2010 in surface seawater. Seasonality and seasonal amplitude are analogous in both time-series, with seasonality in pHT in situ (pH at in situ seawater conditions on the total hydrogen ion scale) primarily determined by seasonality in sea surface temperature. The evaluated pHT in situ trends at BBMO (-0.0021 ± 0.0003 yr-1) and EOS (-0.0028 ± 0.0005 yr-1) agree with those reported for coastal and open ocean surface waters in the Mediterranean Sea and open ocean surface waters of the global ocean, therefore indicating that these time-series are representative of global ocean acidification signals despite being coastal. The decreases in pHT in situ can be attributed to increases in total dissolved inorganic carbon (DIC; 1.5 ± 0.4 µmol kg-1 yr-1 at BBMO and 1.6 ± 0.6 µmolESkg-1 yr-1 at EOS) and sea surface temperature (0.08 ± 0.02℃ yr-1 at BBMOand 0.08 ± 0.04℃ yr-1 at EOS). The increases in carbon dioxide fugacity (fCO2; 2.4 ± 0.3 µmol kg-1 yr-1 at BBMO and 2.9 ± 0.6 µmol kg-1 yr-1 at EOS) follow the atmospheric CO2 forcing, thus indicating the observed DIC increase is related to anthropogenic CO2 uptake. The increasing trends in TA (1.2 ± 0.3 µmol kg-1 yr-1 at BBMO and 1.0 ± 0.5 µmol kg-1 yr-1 at EOS) buffered the acidification rates, counteracting 60% and 72% of the pHT in situ decrease caused by increasing DIC at EOS and BBMO, respectively. Once accounted for the neutralizing effect of TA increase, the rapid sea surface warming plays a larger role in the observed pH decreases (43% at EOS and 62% at BBMO) than the DIC increase (36% at EOS and 33% at BBMO). [ABSTRACT FROM AUTHOR]

In this work, we present, for the first time, the seawater carbonate system measurements of two coastal time-series in the NW Mediterranean Sea, L’Estartit Oceanographic Station (EOS; 42.05°N 3.2542°E) and the Blanes Bay Microbial Observatory (BBMO; 41.665°N 2.805°E). At these two time-series, measurements of total alkalinity (TA), pH, and associated variables, such as dissolved inorganic nutrients, temperature, and salinity, have been performed monthly since 2010 in surface seawater. Seasonality and seasonal amplitude are analogous in both time-series, with seasonality in pHTin situ(pH at in situ seawater conditions on the total hydrogen ion scale) primarily determined by seasonality in sea surface temperature. The evaluated pHTin situtrends at BBMO (-0.0021 ± 0.0003 yr-1) and EOS (-0.0028 ± 0.0005 yr-1) agree with those reported for coastal and open ocean surface waters in the Mediterranean Sea and open ocean surface waters of the global ocean, therefore indicating that these time-series are representative of global ocean acidification signals despite being coastal. The decreases in pHTin situcan be attributed to increases in total dissolved inorganic carbon (DIC; 1.5 ± 0.4 µmol kg-1 yr-1 at BBMO and 1.6 ± 0.6 µmolESkg-1 yr-1 at EOS) and sea surface temperature (0.08 ± 0.02 °C yr-1 at BBMO and 0.08 ± 0.04 °C yr-1 at EOS). The increases in carbon dioxide fugacity (fCO2; 2.4 ± 0.3 µmol kg-1 yr-1 at BBMO and 2.9 ± 0.6 µmol kg-1 yr-1 at EOS) follow the atmospheric CO2 forcing, thus indicating the observed DIC increase is related to anthropogenic CO2 uptake. The increasing trends in TA (1.2 ± 0.3 µmol kg-1 yr-1 at BBMO and 1.0 ± 0.5 µmol kg-1 yr-1 at EOS) buffered the acidification rates, counteracting 60% and 72% of the pHTin situdecrease caused by increasing DIC at EOS and BBMO, respectively. Once accounted for the neutralizing effect of TA increase, the rapid sea surface warming plays a larger role in the observed pH decreases (43% at EOS and 62% at BBMO) than the DIC increase (36% at EOS and 33% at BBMO).

The problem of ocean acidification caused by the increase of atmospheric carbon dioxide concentration is becoming increasingly prominent. Field observation in the northwest Pacific Ocean was carried out along the 150°E transect in November 2019. The distribution characteristics and influencing factors of the surface seawater carbonate chemistry, including dissolved inorganic carbon (DIC), total alkalinity (TA), pH, partial pressure of carbon dioxide (pCO2) and aragonite saturation state (Ωarag) were investigated. DIC and TA ranged from 1915 to 2014 µmol kg−1 and 2243 to 2291 µmol kg−1, respectively; DIC in general decreased with decreasing latitude, but TA had no clear latitudinal gradient. pCO2 values increased with the decrease of latitude and were all below the atmospheric pCO2 level, ranging from 332 to 387 µatm. pH on the total hydrogen ion concentration scale (pHT) decreased with the decrease of latitude in the range of 8.044–8.110, while Ωarag increased with the decrease of latitude in the range of 2.61–3.88, suggesting that the spatial distributions of pHT and Ωarag were out of phase. Compared with the present, the predicted values of pHT and Ωarag by the end of this century would decrease remarkedly; larger declines were found in the higher pHT and Ωarag regions, resulting in the differences along the meridional gradient becoming smaller for both pHT and Ωarag. [ABSTRACT FROM AUTHOR]

The red algae Gracilariopsis lemaneiformis is extensively cultivated at high densities, leading to significant increases in regional seawater pH due to its photosynthetic removal of inorganic carbon. We conducted a study on G. lemaneiformis cultured under various pH conditions (normal pH, pH 9.3, and pH 9.6) and light levels (dark and 100 μmol photons m -2  s -1 ) to investigate how high pH seawater environments affect the metabolic processes of G. lemaneiformis. The high pH did not directly damage the photosynthetic light reactions or the Calvin cycle. Instead, the observed reduction in photosynthetic rates was primarily due to CO 2 limitation. However, under illuminated conditions, a high pH environment leads to a decrease in electron transport efficiency (ETo/RC) and reaction center density (RC/CSo), while simultaneously increasing the levels of hydrogen peroxide (H 2 O 2 ), malondialdehyde (MDA), and the activity of antioxidant enzymes. Under illuminated conditions, the limitation of inhibit the photosynthetic electron transport process, leading to energy imbalance and excessive production of reactive oxygen species, which in turn resulted in lipid peroxidation of the cell membrane. This might be one of the inducing factors responsible for the bleaching in sea-farmed G. lemaneiformis plants., (© 2024 American Society for Photobiology.)

An event of releasing untreated effluent caused serious decreases in surface seawater pH from 8.1 to lower than 7.5 in seven years and increased back to prior levels after 15 years. It gives us a rare natural experiment to examine the impacts of decreases in pH on the marine plankton communities (phytoplanktons, zooplanktons, shrimp larvae, crab larvae, fish eggs, and larvae) in the natural environment. Observed decreases in pH had a nonlinear effect ubiquitous on all plankton groups, leading to a reduction of approximately 50 % in their density and abundance compared to the level at pH 8.1. Non-linear responses of planktons implied the existence of specific groups more robust to decreases in pH. As pH bounced back to normal levels, the density and abundance of the plankton communities also recovered, further indicating that the negative impacts of decreases in pH on the marine plankton communities were reversible., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

The impact of increasing atmospheric CO2 and the resulting decreasing pH of seawater are in the focus of current environmental research. These factors cause problems for marine calcifiers such as reduced calcification rates and the dissolution of calcareous skeletons. While the impact on recent organisms is well established, little is known about long-term evolutionary consequences. Here, we assessed whether ammonoids reacted to environmental change by changing septal thickness. We measured the septal thickness of ammonoid phragmocones through ontogeny in order to test the hypothesis that atmospheric pCO2, seawater pH and other factors affected aragonite biomineralisation in ammonoids. Particularly, we studied septal thickness of ammonoids before and after the ocean acidification event in the latest Triassic until the Early Cretaceous. Early Jurassic ammonoid lineages had thinner septa relative to diameter than their Late Triassic relatives, which we tentatively interpret as consequence of a positive selection for reduced shell material as an evolutionary response to this ocean acidification event. This response was preserved within several lineages among the Early Jurassic descendants of these ammonoids. By contrast, we did not find a significant correlation between septal thickness and long-term atmospheric pCO2 or seawater pH, but we discovered a correlation with palaeolatitude. [ABSTRACT FROM AUTHOR]

Boron systematics offer a unique opportunity to reveal coral calcifying fluid (CF) chemistry and seawater pH (pHsw). Here, we assess the intercolony differences of skeletal δ11B and B/Ca, and examine their variation in modern and fossil Porites spp. collected from the east Hainan Island in the northern South China Sea (SCS), to explore changes in coral CF chemistry and pHsw over the last millennium. This enables us to assess whether ocean acidification (OA) has disturbed the ability of corals to control their CF chemistry, and whether splicing coral δ11B‐pH records can trace long‐term pHsw variability. We demonstrate that coral boron systematics bear remarkable intercolony differences, with mean offset as high as 1.05‰ for δ11B and 183.1 μmol/mol for B/Ca. With this in mind, we show that fossil corals exhibit no significant difference in their CF carbonate chemistry, but all have systematically higher CF pH (pHcf, by an average of 0.12 units) and almost equivalent CF dissolved inorganic carbon (DICcf) concentration, compared to modern corals. This suggests greater OA impacts on coral pHcf but less noticeable effects on DICcf. In addition, the ∼0.12 decline in pHcf translates to about 0.24 reduction in pHsw, similar to another coral‐based estimate (∼0.24) from south Hainan Island, corroborating significant OA in the northern SCS since the industrial era. Nevertheless, we find that pHsw in the east Hainan Island has staged a recovery from 1980 to 2010, slowing down the OA pace, highlighting important roles of other local forcing on pHsw regulation. Key Points: Coral boron systematics bear considerable intercolony differencesFossil corals aged within the past 1 ka have higher pHcf but equivalent DICcf levels compared to the modern coralsSignificant post‐industrial pHsw decline occurred in the northern South China Sea [ABSTRACT FROM AUTHOR]

Chemical changes in the diffusive boundary layer (DBL) generated by photosynthesising macroalgae are expected to play an important role in modulating the effects of ocean acidification (OA), but little is known about the effects on early life stages of marine invertebrates in modified DBLs. Larvae that settle to macroalgal surfaces and remain within the DBL will experience pH conditions markedly different from the bulk seawater. We investigated the interactive effects of seawater pH and DBL thickness on settlement and early post-settlement growth of the sea urchin Pseudechinus huttoni, testing whether coralline-algal DBLs act as an environmental buffer to OA. DBL thickness and pH levels (estimated from well-established relationships with oxygen concentration) above the crustose coralline algal surfaces varied with light availability (with photosynthesis increasing pH to as high as pH 9.0 and respiration reducing pH to as low as pH 7.4 under light and dark conditions, respectively), independent of bulk seawater pH (7.5, 7.7, and 8.1). Settlement success of P. huttoni increased over time for all treatments, irrespective of estimated pH in the DBL. Juvenile test growth was similar in all DBL manipulations, showing resilience to variable and low seawater pH. Spine development, however, displayed greater variance with spine growth being negatively affected by reduced seawater pH in the DBL only in the dark treatments. Scanning electron microscopy revealed no observable differences in structural integrity or morphology of the sea urchin spines among pH treatments. Our results suggest that early juvenile stages of P. huttoni are well adapted to variable pH regimes in the DBL of macroalgae across a range of bulk seawater pH treatments.

The increases of atmospheric carbon dioxide and other greenhouse gases have caused fundamental changes to the physical and biogeochemical properties of the oceans, and it will continue to occur in the foreseeable future. Based on the outputs of nine Earth System Models from the fifth phase of the Coupled Model Intercomparison Project (CMIP5), in this study, we provided a synoptic assessment of future changes in the sea surface temperature (SST), salinity, dissolved oxygen (DO), seawater pH, and marine net primary productivity (NPP) in the coastal China seas over the 21st century. The results show that the mid-high latitude areas of the coastal China seas (East China Seas (ECS), including the Bohai Sea, Yellow Sea, and East China Sea) will be simultaneously exposed to enhanced warming, deoxygenation, acidification, and decreasing NPP as a consequence of increasing greenhouse gas emissions. The magnitudes of the changes will increase as the greenhouse gas concentrations increase. Under the high emission scenario (Representative Concentration Pathway 8.5), the ECS will experience an SST increase of 3.24±1.23°C, a DO concentration decrease of 10.90±3.92 µmol/L (decrease of 6.3%), a pH decline of 0.36±0.02, and a NPP reduction of −17.7±6.2 mg/(m2·d) (decrease of 12.9%) relative to the current levels (1980–2005) by the end of this century. The co-occurrence of these changes and their cascade effects are expected to induce considerable biological and ecological responses, thereby making the ECS among the most vulnerable ocean areas to future climate change. Despite high uncertainties, our results have important implications for regional marine assessments. [ABSTRACT FROM AUTHOR]

Coral polyps have a fluid-filled internal compartment, the gastrovascular cavity (GVC). Respiration and photosynthesis cause large daily excursions in GVC oxygen concentration (O2) and pH, but few studies have examined how this correlates with calcification rates. We hypothesized that GVC chemistry can mediate and ameliorate the effects of decreasing seawater pH (pHSW) on coral calcification. Microelectrodes were used to monitor O2 and pH within the GVC of Montastraea cavernosa and Duncanopsammia axifuga (pH only) in both the light and the dark, and three pHSW levels (8.2, 7.9, and 7.6). At pHSW 8.2, GVC O2 ranged from ca. 0 to over 400% saturation in the dark and light, respectively, with transitions from low to high (and vice versa) within minutes of turning the light on or off. For all three pHSW treatments and both species, pHGVC was always significantly above and below pHSW in the light and dark, respectively. For M. cavernosa in the light, pHGVC reached levels of pH 8.4–8.7 with no difference among pHSW treatments tested; in the dark, pHGVC dropped below pHSW and even below pH 7.0 in some trials at pHSW 7.6. For D. axifuga in both the light and the dark, pHGVC decreased linearly as pHSW decreased. Calcification rates were measured in the light concurrent with measurements of GVC O2 and pHGVC. For both species, calcification rates were similar at pHSW 8.2 and 7.9 but were significantly lower at pHSW 7.6. Thus, for both species, calcification was protected from seawater acidification by intrinsic coral physiology at pHSW 7.9 but not 7.6. Calcification was not correlated with pHGVC for M. cavernosa but was for D. axifuga. These results highlight the diverse responses of corals to changes in pHSW, their varying abilities to control pHGVC, and consequently their susceptibility to ocean acidification. [ABSTRACT FROM AUTHOR]

Understanding the way in which a decline in ocean pH can affect calcareous organisms could enhance our ability to predict the impacts of the potential decline in seawater pH on marine ecosystems, and could help to reconstruct the paleoceanographic events over a geological time scale. Planktic foraminifera are among the most important biological proxies for these studies; however, the existing research on planktic foraminifera is almost exclusively based on their geochemical indices, without the inclusion of information on their biological development. Through a series of on-board experiments in the western tropical Pacific (134°33′54″ E, 12°32′47″ N), the present study showed that the symbiont-bearing calcifier Trilobatus sacculifer—a planktic foraminifer—responded rapidly to a decline in seawater pH, including losing symbionts, bleaching, etc. Several indices were established to quantify the relationships between these biological parameters and seawater pH, which could be used to reconstruct the paleoceanographic seawater pH. We further postulated that the loss of symbionts in planktic foraminifera acts as an adaptive response to the stress of low pH. Our results indicate that an ongoing decline in seawater pH may hinder the growth and calcification of planktic foraminifera by altering their biological processes. A reduction in carbonate deposition and predation could have profound effects on the carbon cycle and energy flow in the marine food web.

Coral reef community composition, function, and resilience have been altered by natural and anthropogenic stressors. Future anthropogenic ocean and coastal acidification (together termed “acidification”) may exacerbate this reef degradation. Accurately predicting reef resilience requires an understanding of not only direct impacts of acidification on marine organisms but also indirect effects on species interactions that influence community composition and reef ecosystem functions. In this 28-day experiment, we assessed the effect of acidification on coral–algal, coral–sponge, and algal–sponge interactions. We quantified growth of corals (Siderastrea radians), fleshy macroalgae (Dictyota spp.), and sponges (Pione lampa) that were exposed to local summer ambient (603 μatm) or elevated (1105 μatm) pCO2 seawater. These species are common to hard-bottom communities, including shallow reefs, in the Florida Keys. Each individual was maintained in isolation or paired with another organism. Coral growth (net calcification) was similar across seawater pCO2 and interaction treatments. Fleshy macroalgae had increased biomass when paired with a sponge but lost biomass when growing in isolation or paired with coral. Sponges grew more volumetrically in the elevated seawater pCO2 treatment (i.e., under acidification conditions). Although these results are limited in temporal and spatial scales due to the experimental design, they do lend support to the hypothesis that acidification may facilitate a shift towards increased sponge and macroalgae abundance by directly benefiting sponge growth which in turn may provide more dissolved inorganic nitrogen to macroalgae in the Florida Keys.

Accurate spectrophotometric pH measurements in seawater are critical to documenting long-term changes in ocean acidity and carbon chemistry, and for calibration of autonomous pH sensors. The recent development of purified indicator dyes greatly improved the accuracy of spectrophotometric pH measurements by removing interfering impurities that cause biases in pH that can grow over the seawater pH range to > 0.01 above pH 8. However, some batches of purified indicators still contain significant residual impurities that lead to unacceptably large biases in pH for oceanic and estuarine climate quality measurements. While high-performance liquid chromatography (HPLC) is the standard method for verifying dye purity, alternative approaches that are simple to implement and require less specialized equipment are desirable. We developed a model to detect impurities in the pH indicator m- cresol purple (m CP) using a variant of the classification technique Soft Independent Modeling of Class Analogy (SIMCA). The classification model was trained with pure m CP spectra (350 nm to 750 nm at 1 nm resolution) at pH 12 and tested on independent samples of unpurified and purified m CP with varying levels of impurities (determined by HPLC) and measured on two different spectrophotometers. All the dyes identified as pure by the SIMCA model were sufficiently low in residual impurities that their apparent biases in pH were < 0.002 in buffered artificial seawater solutions at a salinity of 35 and over a pH range of 7.2 to 8.2. Other methods that can also detect residual impurities relevant to climate quality measurements include estimating the impurity absorption at 434 nm and assessing the apparent pH biases relative to a reference purified dye in buffered solutions or natural seawater. Laboratories that produce and distribute purified m CP should apply the SIMCA method or other suitable methods to verify that residual impurities do not significantly bias pH measurements. To apply the SIMCA method, users should download the data and model developed in this work and measure a small number of instrument standardization and model validation samples. This method represents a key step in the development of a measurement quality framework necessary to attain the uncertainty goals articulated by the Global Ocean Acidification Observing Network (GOA-ON) for climate quality measurements (i.e., ±0.003 in pH). • We developed a chemometric model to detect impurities in a pH indicator dye. • The model was developed for m -cresol purple, a widely used dye for seawater pH. • The model can verify a dye is pure enough for "climate quality" pH measurements. • Other spectrophotometric methods can also be used to assess dye purity. [ABSTRACT FROM AUTHOR]

Upwelling phenomena alter the physical and chemical parameters of the sea's subsurface waters, producing low levels of temperature, pH and dissolved oxygen, which can seriously impact the early developmental stages of marine organisms. To understand how upwelling can affect the encapsulated development of the gastropod Acanthina monodon, capsules containing embryos at different stages of development (initial, intermediate and advanced) were exposed to upwelling conditions (pH = 7.6; O 2 = 3 mg L−1; T° = 9 °C) for a period of 7 days. Effects of treatment were determined by estimating parameters such as time to hatching, number of hatchlings per capsule, percentage of individuals with incomplete development, and shell parameters such as shell shape and size, shell strength, and the percentage of the organic/inorganic content. We found no significant impacts on hatching time, number of hatchlings per capsule, or percentage of incomplete development in either the presence or absence of upwelling, regardless of developmental stage. On the other hand, latent effects on encapsulated stages of A. monodon were detected in embryos that had been exposed to upwelling stress in the initial embryonic stage. The juveniles from this treatment hatched at smaller sizes and with higher organic content in their shells, resulting in a higher resistance to cracking 30 days after hatching, due to greater elasticity. Geometric morphometric analysis showed that exposure to upwelling condition induced a change in the morphology of shell growth in all post-hatching juveniles (0–30 days), regardless of embryonic developmental stage at the time of exposure. Thus, more elongated shells (siphonal canal and posterior region) and more globular shells were observed in newly hatched juveniles that had been exposed to the upwelling condition. The neutral or even positive upwelling exposure results suggests that exposure to upwelling events during the encapsulated embryonic phase of A. monodon development might not have major impacts on the future juvenile stages. However, this should be taken with caution in consideration of the increased frequency and intensity of upwelling events predicted for the coming decades. • More advanced embryos exposed to upwelling conditions delayed the time to hatching. • Juveniles that hatched at smaller sizes were more resistant to cracking. • Exposure of encapsulated embryos to upwelling conditions altered the juvenile morphology. • Latent effects were found mainly when embryos were exposed to upwelling stress during initial stages of development. [ABSTRACT FROM AUTHOR]

Research assessing the biological impacts of global ocean change often requires a burdensome characterization of seawater carbonate chemistry. For laboratory-based ocean acidification research, this impedes the scope of experimental design. Honeywell Durafet® III pH electrodes provide precise and continuous seawater pH measurements. In addition to use in oceanographic sensor packages, Durafets can also be used in the laboratory to track and control seawater treatments via Honeywell Universal Dual Analyzers (UDAs). Here we provide performance data, instructions, and step-by-step recommendations for use of multiple UDA-Durafets. Durafet pH measurements were within ±0.005 units pHT of spectrophotometric measurements and agreement among eight Durafets was better than ±0.005 units pHT. These results indicate equal performance to Durafets in oceanographic sensor packages, but methods for calibration and quality control differ. Use of UDA-Durafets vastly improves time-course documentation of experimental conditions and reduces person-hours dedicated to this activity. Due to the versatility of integrating Durafets in laboratory seawater systems, this technology opens the door to advance the scale of questions that the ocean acidification research community aims to address.

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; 1 σ = ±17 μmol kg) 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 ( pCO), and pH from a surface mooring on the outer coast of Washington. In situ pCO 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 pCO-pH time series. [ABSTRACT FROM AUTHOR]

Five tropical seaweeds, Kappaphycus alvarezii (Doty) Doty ex P.C. Silva, Padina australis Hauck, Sargassum binderi Sonder ex J. Agardh (syn. S. aquifolium (Turner) C. Agardh), Sargassum siliquosum J. Agardh and Turbinaria conoides (J. Agardh) Kützing, were incubated in seawater of pH 8.0, 7.8 (ambient), 7.6, 7.4 and 7.2, to study the effects of changing seawater pH on halocarbon emissions. Eight halocarbon species known to be emitted by seaweeds were investigated: bromoform (CHBr3), dibro­momethane (CH2Br2), iodomethane (CH3I), diiodomethane (CH2I2), bromoiodomethane (CH2BrI), bromochlorometh­ane (CH2BrCl), bromodichloromethane (CHBrCl2), and dibro­mochloromethane (CHBr2Cl). These very short-lived halocarbon gases are believed to contribute to stratospheric halogen concentrations if released in the tropics. It was observed that the seaweeds emit all eight halocarbons assayed, with the exception of K. alvarezii and S. binderi for CH2I2 and CH3I respectively, which were not measurable at the achievable limit of detection. The effect of pH on halocarbon emission by the seaweeds was shown to be species-specific and compound specific. The highest percentage changes in emissions for the halocarbons of interest were observed at the lower pH levels of 7.2 and 7.4 especially in Padina australis and Sargassum spp., showing that lower seawater pH causes elevated emissions of some halocarbon compounds. In general the seaweed least affected by pH change in terms of types of halocarbon emission, was P. australis. The commercially farmed seaweed K. alvarezii was very sensitive to pH change as shown by the high increases in most of the compounds in all pH levels relative to ambient. In terms of percentage decrease in maximum quantum yield of photosynthesis (Fv∕Fm) prior to and after incubation, there were no significant correlations with the various pH levels tested for all seaweeds. The correlation between percentage decrease in the maximum quantum yield of photosynthesis (Fv∕Fm) and halocarbon emission rates, was significant only for CH2BrCl emission by P. australis (r = 0.47; p ≤ 0.04), implying that photosynthesis may not be closely linked to halocarbon emissions by the seaweeds studied. Bromine was the largest contributor to the total mass of halogen emitted for all the seaweeds at all pH. The highest total amount of bromine emitted by K. alvarezii (an average of 98% of total mass of halogens) and the increase in the total amount of chlorine with decreasing seawater pH fuels concern for the expanding seaweed farming activities in the ASEAN region.

Increasing atmospheric CO2 concentrations are resulting in a reduction in seawater pH, with potential detrimental consequences for marine organisms. Improved efforts are required to monitor the anthropogenically driven pH decrease in the context of natural pH variations. We present here a high resolution surface water pH data set obtained in summer 2011 in North West European Shelf Seas. The aim of our paper is to demonstrate the successful deployment of the pH sensor, and discuss the carbonate chemistry dynamics of surface waters of Northwest European Shelf Seas using pH and ancillary data. The pH measurements were undertaken using spectrophotometry with a Lab-on-Chip pH sensor connected to the underway seawater supply of the ship. The main processes controlling the pH distribution along the ship’s transect, and their relative importance, were determined using a statistical approach. The pH sensor allowed 10 measurements h−1 with a precision of 0.001 pH units and a good agreement with pH calculated from a pair of discretely sampled carbonate variables dissolved inorganic carbon (DIC), total alkalinity (TA) and partial pressure of CO2 (pCO2) (e.g., pHDICpCO2). For this summer cruise, the biological activity formed the main control on the pH distribution along the cruise transect. This study highlights the importance of high quality and high resolution pH measurements for the assessment of carbonate chemistry dynamics in marine waters.

Changing ocean temperatures are predicted to challenge marine organisms, especially when combined with other factors, such as ocean acidification. Acclimation, as a form of phenotypic plasticity, can moderate the consequences of changing environments for biota. Our understanding of how altered temperature and acidification together influence species' acclimation responses is, however, limited compared with that of responses to single stressors. This study investigated how temperature and acidification affect the thermal tolerance and righting speed of the girdled dogwhelk, Trochia cingulata. Whelks were acclimated for 2 weeks to combinations of three temperatures (11°C: cold, 13°C: moderate and 15°C: warm) and two pH regimes (8.0: moderate and 7.5: acidic). We measured the temperature sensitivity of the righting response by generating thermal performance curves from individual data collected at seven test temperatures and determined critical thermal minima (CTmin) and maxima (CTmax). We found that T. cingulata has a broad basal thermal tolerance range (∼38°C) and after acclimation to the warm temperature regime, both the optimal temperature for maximum righting speed and CTmax increased. Contrary to predictions, acidification did not narrow this population's thermal tolerance but increased CTmax. These plastic responses are likely driven by the predictable exposure to temperature extremes measured in the field which originate from the local tidal cycle and the periodic acidification associated with ocean upwelling in the region. This acclimation ability suggests that T. cingulata has at least some capacity to buffer the thermal changes and increased acidification predicted to occur with climate change., Competing Interests: Competing interests The authors declare no competing or financial interests., (© 2023. Published by The Company of Biologists Ltd.)

Equimolar Tris (2-amino-2-hydroxymethyl-propane-1,3-diol) buffer prepared in artificial seawater media is a widely accepted pH standard for oceanographic pH measurements, though its change in pH over pressure is largely unknown. The change in volume (Δ V ) of dissociation reactions can be used to estimate the effects of pressure on the dissociation constant of weak acid and bases. The Δ V of Tris in seawater media of salinity 35 (Δ V Tris ⁎ ) was determined between 10 and 30 °C using potentiometry. The potentiometric cell consisted of a modified high pressure tolerant Ion Sensitive Field Effect Transistor pH sensor and a Chloride-Ion Selective Electrode directly exposed to solution. The effects of pressure on the potentiometric cell were quantified in aqueous HCl solution prior to measurements in Tris buffer. The experimentally determined Δ V Tris ⁎ were fitted to the equation Δ V Tris ⁎ = 4.528 + 0.04912 t where t is temperature in Celsius; the resultant fit agreed to experimental data within uncertainty of the measurements, which was estimated to be 0.9 cm − 3 mol − 1 . Using the results presented here, change in pH of Tris buffer due to pressure can be constrained to better than 0.003 at 200 bar, and can be expressed as: ∆ pH Tris = − 4.528 + 0.04912 t P ln 10 RT . where T is temperature in Kelvin, R is the universal gas constant (83.145 cm 3 bar K − 1 mol − 1 ), and P is gauge pressure in bar. On average, pH of Tris buffer changes by approximately − 0.02 at 200 bar. [ABSTRACT FROM AUTHOR]

Sub-sea geological storage of carbon dioxide (CO 2 ) provides a viable option for the Carbon Capture and Storage (CCS) approach for reducing atmospheric emissions of this greenhouse gas. Although generally considered to offer a low risk of major leakage, it remains relevant to establish the possible consequences for marine organisms that live in or on sediments overlying these storage areas if such an event may occur. The present study has used a series of laboratory exposures and behavioral bioassays to establish the sensitivity of Arctica islandica to simulated leakages of CO 2 . This long-lived bivalve mollusc is widely distributed throughout the North Sea, an area where geological storage is currently taking place and where there are plans to expand this operation significantly. A recently published model has predicted a maximum drop of 1.9 pH units in seawater at the point source of a substantial escape of CO 2 from sub-sea geological storage in this region. Valve movements of A. islandica exposed to reduced pH seawater were recorded continuously using Hall effect proximity sensors. Valve movement regulation is important for optimising the flow of water over the gills, which supplies food and facilitates respiration. A stepwise reduction in seawater pH showed an initial increase in both the rate and extent of valve movements in the majority of individuals tested when pH fell to 6.2 units. Exposing A. islandica to pH 6.2 seawater continuously for seven days resulted in a clear increase in valve movements during the first 40 h of exposure, followed by a gradual reduction in activity intensity over the subsequent five days, suggesting acclimation. The ability of both exposed and control bivalves to burrow successfully into sediment on completion of this exposure was very similar. A final exposure trial, testing whether increased valve movements initiated by reduced pH were related to foot extension during attempted burrowing, found no such association. In summary, significant changes in valve behavior did not occur until seawater pH fell to 6.2 units. The response took the form of an increase in valve activity rather than closure. The absence of foot extension coincident with increased valve movements indicates A. islandica were not attempting to burrow, leaving the possibility that valve movements are supporting a respiratory response to hypercapnia. In conclusion, A. islandica appears to be tolerant of reductions in seawater pH equivalent to those predicted for substantial losses of CO 2 through leakage from sub-sea geological storage. [ABSTRACT FROM AUTHOR]

Anthropogenic carbon dioxide (CO2) emissions simultaneously increase ocean temperatures and reduce ocean surface pH, a process termed ocean acidification (OA). OA is expected to negatively affect the growth and physiology of many calcified organisms, but the response of non-calcified (fleshy) organisms is less well understood. Rising temperatures and pCO2 can enhance photosynthetic rates (within tolerance limits). Therefore, warming may interact with OA to alter biological responses of macroalgae in complicated ways. Beyond thresholds of physiological tolerance, however, rising temperatures could further exacerbate negative responses to OA. Many studies have investigated the effects of OA or warming independently of each other, but few studies have quantified the interactive effects of OA and warming on marine organisms. We conducted four short-term independent factorial CO2 enrichment and warming experiments on six common species of calcified and fleshy macroalgae from southern California to investigate the independent and interactive effects of CO2 and warming on growth, carbonic anhydrase (CA) enzyme activity, pigment concentrations, and photosynthetic efficiency. There was no effect of elevated pCO2 on CA activity, pigment concentration, and photosynthetic efficiency in the macroalgal species studies. However, we found that calcareous algae suffered reduced growth rates under high pCO2 conditions alone, although the magnitude of the effect varied by species. Fleshy algae had mixed responses of growth rates to high pCO2, indicating that the effects of pCO2 enrichment are inconsistent across species. The combined effects of elevated pCO2 and warming had a significantly negative impact on growth for both fleshy and calcareous algae; calcareous algae experienced five times more weight loss than specimens in ambient control conditions and fleshy growth was reduced by 76%. Our results demonstrate the need to study the interactive effects of multiple stressors associated with global change on marine communities. [ABSTRACT FROM AUTHOR]

The apparent molal volumes and compressibilities of Tris and Tris–HCl have been determined in water (5–45 °C) and 0.725 m NaCl (5–25 °C). The changes in the volume (Δ V ) and compressibility (Δ κ ) for the dissociation of Tris–H + Tris - H + = Tris + H + as functions of temperature in water and 0.725 m NaCl have been determined from these measurements. The values of Δ V and Δ κ have been used to determine the effect of pressure on the dissociation constant for Tris–H + ( K P / K 0 ). ln ( K P / K 0 ) = - ∆ V / ( R T ) P + 0 .5∆ k / ( R T ) P 2 These results will be useful in the calibration of pH systems making in-situ measurements at high pressure in seawater. In 0.725 m NaCl at 5 °C and a pressure of 2000 bar, the dissociation constant is reduced by 29%. [ABSTRACT FROM AUTHOR]

Abstract: The boron isotopic composition of biogenic carbonates has been used to reconstruct seawater pH and atmospheric pCO2 on Pleistocene and Cenozoic timescales. Because of their excellent preservation and extensive fossil record throughout the Phanerozoic, brachiopods are a promising candidate for extending the boron isotope record as far back as the Cambrian. Here we present stable carbon, oxygen, and boron isotopic measurements of modern Terebratulid brachiopod calcite in comparison with environmental pH estimates calculated from oceanographic data. Geochemical transects along the length and depth of single shells confirm previously published trends in carbon and oxygen isotopic composition. In the outer surface (primary and outermost secondary layers), δ11B covaries with δ13C and δ18O, with more negative values in the outer and more positive values in the middle of the shell. However, δ11B deviates from δ13C and δ18O in the inner part of the secondary layer, where the δ13C and δ18O values are more positive and near equilibrium, whereas δ11B returns to more negative values. A comparison of different specimens of the species Terebratalia transversa (Sowerby, 1846) and Laqueus californianus (Küster, 1844) microsampled from the middle part of the fibrous secondary layer demonstrates a clear correlation to ambient pH with a sensitivity similar to other empirical calibration curves for cultured planktic foraminifers, corals, and inorganic calcite. The relationship in other species is less clear and significantly offset, necessitating the use of a single species or a cross-calibration method with other species in paleo-pH reconstructions. [Copyright &y& Elsevier]

Abstract: The ratio of boron to calcium (B/Ca) in the calcite tests of planktic foraminifers may serve as a proxy for past seawater chemistry, but controls on B incorporation are not yet certain. Here we present the results of laboratory culture experiments with live specimens of Globigerinoides ruber (pink) and Globigerinoides sacculifer, which provide new insight into B incorporation controls. We find that in G. sacculifer, B/Ca increases with increasing pH (lower [HCO3 −], higher [CO3 2−] and [B(OH)4 −]), but decreases with increasing total dissolved inorganic carbon (DIC) (higher [HCO3 −] and [CO3 2−], constant [B(OH)4 −]). This suggests competition between aqueous boron and carbon species for inclusion into the calcite lattice. Similar to previous experiments with the subtropical-temperate Orbulina universa, B/Ca increases with salinity, but not with temperature. We evaluate possible carbonate system control parameters, and compare our tropical culture calibrations with new and published core–top data. [Copyright &y& Elsevier]

Abstract: This study examines the utility of combining pH measurements with other inorganic carbon parameters for autonomous mooring-based carbon cycle research. Determination of the full suite of inorganic carbon species in the oceans has previously been restricted to ship-based studies. Now with the availability of autonomous sensors for pH and the partial pressure of CO2 (pCO2), it is possible to characterize the inorganic carbon system on moorings and other unmanned platforms. The indicator-based pH instrument, SAMI-pH, was deployed with an autonomous equilibrator-infrared pCO2 system in Monterey Bay, California USA from June to August 2007. The two-month time-series show a high degree of short-term variability, with pH and pCO2 changing by as much as 0.32 pH units and 240μatm, respectively, during upwelling periods. The pH and salinity-derived alkalinity (ATsalin) were used to calculate the other inorganic carbon parameters, including pCO2, total dissolved inorganic carbon (DIC) and CaCO3 saturation states. The calculated pCO2 was within 2μatm of the measured pCO2 during the first day of the deployment and within 8μatm over the first month. The DIC calculated from pH–ATsalin and pCO2–ATsalin were within 5μmolkg−1 of each other during the first month. However, DIC calculated from pH–pCO2 differed by ~50μmolkg−1 from the other estimates over the same period, reflecting the sensitivity of the pH–pCO2 calculation to measurement error. The data continued to diverge during the final month and this difference was likely driven by extensive biofouling. Because of the relative insensitivity of CO3 2− concentration to these errors, aragonite saturation calculated from the pH–pCO2 pair was within 0.15 of the pH–ATsalin values over the entire deployment. These results show that in situ pH, when combined with other CO2 parameters, can provide valuable insights into both data quality and inorganic carbon cycling. [Copyright &y& Elsevier]

Abstract: Boron isotopic and elemental systematics are used to define the vital effects for the temperate shallow water Mediterranean coral Cladocora caespitosa. The corals are from a range of seawater pH conditions (pHT ~7.6 to ~8.1) and environmental settings: (1) naturally living colonies harvested from normal pH waters offshore Levanto, (2) colonies transplanted nearby a subsea volcanic vent system, and (3) corals cultured in aquaria exposed to high (700μatm) and near present day (400μatm) pCO2 levels. B/Ca compositions measured using laser ablation inductively coupled mass spectrometry (LA-ICPMS) show that boron uptake by C. caespitosa cultured at different pCO2 levels is independent of ambient seawater pH being mainly controlled by temperature-dependent calcification. In contrast, the boron isotope compositions (δ11Bcarb) of the full suite of corals determined by positive thermal ionisation mass spectrometry (PTIMS) shows a clear trend of decreasing δ11Bcarb (from 26.7 to 22.2‰) with decreasing seawater pH, reflecting the strong pH dependence of the boron isotope system. The δ11Bcarb compositions together with measurements of ambient seawater parameters enable calibration of the boron pH proxy for C. caespitosa, by using a new approach that defines the relationship between ambient seawater pH (pHsw) and the internally controlled pH at the site of calcification (pHbiol). C. caespitosa exhibits a linear relationship between pHsw and the shift in pH due to physiological processes (ΔpH=pHbiol −pHsw) giving the regression ΔpHClad =4.80−0.52×pHsw for this species. We further apply this method (“ΔpH–pHsw”) to calibrate tropical species of Porites, Acropora, and Stylophora reported in the literature. The temperate and tropical species calibrations are all linearly correlated (r 2 >0.9) and the biological fractionation component (ΔpH) between species varies within ~0.2 pH units. Our “ΔpH–pHsw” approach provides a robust and accurate tool to reconstruct palaeoseawater pHsw for both temperate and tropical corals, further validating the boron fractionation factor (αB3–B4 =1.0272) determined experimentally by Klochko et al. (2006) and the boron isotope pH proxy, both of which have been the foci of considerable debate. [Copyright &y& Elsevier]

Current global trends will lead to large-scale changes in climate patterns, ocean circulation and stratification; increased atmospheric CO2 levels will cause acidification of the oceans, with significant impacts on marine biogeochemical cycles and calcareous organisms. In the Mediterranean area, the northern Adriatic Sea is one of the most suitable sites for studying the responses of marine pH to such occurrences because it is the northernmost basin affected by dense water formation during winter, and is also one of the most productive areas in the Mediterranean. The first comparison between two sets of data relating to the dense cold waters of the northern Adriatic, formed in the winters of 1982-1983 and 2007-2008, is presented here. pH values on the Nation Bureau Standard scale from the old dataset have been converted to the 'total hydrogen ion concentration scale' adopted for the new dataset, and are expressed as μmol H[image omitted] . Results at 25 °C show acidification (-0.063 pHT units) and a decrease in carbonate ion concentration (-19.6 μmol H[image omitted] ) in the dense water mass between 1983 and 2008, whereas total alkalinity, carbonate alkalinity, dissolved inorganic carbon and CO2 fugacity exhibit net increases of 74.4, 77.8 and 110.3 μmol H[image omitted] , and 108.3 μatm, respectively, over the same period. [ABSTRACT FROM AUTHOR]

Physiological data and models of coral calcification indicate that corals utilize a combination of seawater bicarbonate and (mainly) respiratory CO2 for calcification, not seawater carbonate. However, a number of investigators are attributing observed negative effects of experimental seawater acidification by CO2 or hydrochloric acid additions to a reduction in seawater carbonate ion concentration and thus aragonite saturation state. Thus, there is a discrepancy between the physiological and geochemical views of coral biomineralization. Furthermore, not all calcifying organisms respond negatively to decreased pH or saturation state. Together, these discrepancies suggest that other physiological mechanisms, such as a direct effect of reduced pH on calcium or bicarbonate ion transport and/or variable ability to regulate internal pH, are responsible for the variability in reported experimental effects of acidification on calcification. To distinguish the effects of pH, carbonate concentration and bicarbonate concentration on coral calcification, incubations were performed with the coral Madracis auretenra (= Madracis mirabilis sensu Wells, 1973) in modified seawater chemistries. Carbonate parameters were manipulated to isolate the effects of each parameter more effectively than in previous studies, with a total of six different chemistries. Among treatment differences were highly significant. The corals responded strongly to variation in bicarbonate concentration, but not consistently to carbonate concentration, aragonite saturation state or pH. Corals calcified at normal or elevated rates under low pH (7.6–7.8) when the seawater bicarbonate concentrations were above 1800 μm. Conversely, corals incubated at normal pH had low calcification rates if the bicarbonate concentration was lowered. These results demonstrate that coral responses to ocean acidification are more diverse than currently thought, and question the reliability of using carbonate concentration or aragonite saturation state as the sole predictor of the effects of ocean acidification on coral calcification. [ABSTRACT FROM AUTHOR]

The impact of CO2-acidified seawater (pH 7.8, 7.6, or 6.5, control = pH 8) on the health of Mytilus edulis was investigated during a 60 d mesocosm experiment. Mussel health was determined using the neutral red retention (NRR) assay for lysosomal membrane stability and from histopathological analysis of reproductive, digestive and respiratory tissues. Seawater acidification was shown to significantly reduce mussel health as measured by the NRR assay, and it is suggested that this impact is due to elevated levels of calcium ions (Ca2+) in the haemolymph, generated by the dissolution of the mussels' calcium carbonate shells. No impact on tissue structures was observed, and it is concluded that M. edulis possess strong physiological mechanisms by which they are able to protect body tissues against short-term exposure to highly acidified seawater. However, these mechanisms come at an energetic cost, which can result in reduced growth during long-term exposures. Consequently, the predicted long-term changes to seawater chemistry associated with ocean acidification are likely to have a more significant effect on the health and survival of M. edulis populations than the short-lived effects envisaged from CO2 leakage from sub-seabed storage. Ocean acidification could reduce the general health status of this commercially and ecologically important marine species. [ABSTRACT FROM AUTHOR]

Abstract: The level and evolution of atmospheric carbon dioxide throughout Earth''s history are key issues for palaeoclimate reconstructions, especially during times of extreme climate change such as those that marked the Neoproterozoic. The carbon isotope ratios of marine carbonates are crucial in the correlation and identification of Neoproterozoic glacial deposits, and they are also used as a record for biogeochemical cycling and potential proxy for atmospheric pCO2. Likewise, the boron and calcium isotope compositions of marine carbonates are potential proxies for palaeo-seawater pH and the ratio of calcium fluxes into and out of seawater, respectively, and together they may be used to estimate atmospheric carbon dioxide. Here we use B and Ca isotopes to estimate palaeoenvironmental conditions in the aftermath of a major Neoproterozoic glaciation in Namibia. The validity of the B and Ca isotope variation in the ancient marine carbonates is evaluated using the oxygen isotope composition of the carbonates and its correlation to the carbon isotope variation. A negative (2.7 to −6.2‰) δ11B excursion occurs in the postglacial carbonates and is interpreted to reflect a temporary decrease in seawater pH. Associated variations in δ44Ca values (ranging between 0.35 and 1.14‰) are linearly coupled with the carbon isotope ratios and imply enhanced postglacial weathering rates. The reconstructed seawater pH and weathering profiles indicates that high atmospheric CO2 concentrations were likely during the melt back of Neoproterozoic glaciations and precipitation of cap carbonates. However, the B isotope trend suggests that these concentrations rapidly ameliorated and they do not co-vary with δ13C. Thus models attempting to link long-lived negative δ13C excursions to elevated pCO2 need to be reconsidered. [Copyright &y& Elsevier]

Simple Summary: The ocean absorbs large amounts of CO2 emitted by human activities, which leads to a decrease in seawater pH, and has the potential to cause damage to calcareous marine organisms. Planktic foraminifera are some of the most important calcareous marine organisms in the ocean, although the biological response of planktic foraminifera to the decline in seawater pH is still unknown. In this study, the biological response of planktic foraminifera to declining seawater pH was studied through a series of on-board experiments. The experimental results showed that the decrease in seawater pH adversely affected the biological processes of planktic foraminifera, resulting in weaker predation, slower growth, lighter shells, and more deformities. In addition, for the first time, we report that microalgae that live with planktic foraminifera were also killed under low-pH conditions. Several indices were established to quantify the relationships between the biological parameters of planktic foraminifera and seawater pH, which could be used to reconstruct the paleoceanographic seawater pH. This study provides experimental data to quantify the biological response of calcareous plankton to a decline in seawater pH. Understanding the way in which a decline in ocean pH can affect calcareous organisms could enhance our ability to predict the impacts of the potential decline in seawater pH on marine ecosystems, and could help to reconstruct the paleoceanographic events over a geological time scale. Planktic foraminifera are among the most important biological proxies for these studies; however, the existing research on planktic foraminifera is almost exclusively based on their geochemical indices, without the inclusion of information on their biological development. Through a series of on-board experiments in the western tropical Pacific (134°33′54″ E, 12°32′47″ N), the present study showed that the symbiont-bearing calcifier Trilobatus sacculifer—a planktic foraminifer—responded rapidly to a decline in seawater pH, including losing symbionts, bleaching, etc. Several indices were established to quantify the relationships between these biological parameters and seawater pH, which could be used to reconstruct the paleoceanographic seawater pH. We further postulated that the loss of symbionts in planktic foraminifera acts as an adaptive response to the stress of low pH. Our results indicate that an ongoing decline in seawater pH may hinder the growth and calcification of planktic foraminifera by altering their biological processes. A reduction in carbonate deposition and predation could have profound effects on the carbon cycle and energy flow in the marine food web. [ABSTRACT FROM AUTHOR]

Simple Summary: This study's data suggest that under the projected scenarios of ocean acidification by 2100 and beyond, significant negative impacts on growth, health, and meat quality are expected, particularly on black sea bream, and will be susceptible to the scientifically approved fish having a weaker resistance to diseases and environmental changes if CO2 emissions in the atmosphere are not curbed. Knowing the expected consequences, mitigation measures are urgently needed. Acidification (OA), a global threat to the world's oceans, is projected to significantly grow if CO2 continues to be emitted into the atmosphere at high levels. This will result in a slight decrease in pH. Since the latter is a logarithmic scale of acidity, the higher acidic seawater is expected to have a tremendous impact on marine living resources in the long-term. An 8-week laboratory experiment was designed to assess the impact of the projected pH in 2100 and beyond on fish survival, health, growth, and fish meat quality. Two projected scenarios were simulated with the control treatment, in triplicates. The control treatment had a pH of 8.10, corresponding to a pCO2 of 321.37 ± 11.48 µatm. The two projected scenarios, named Predict_A and Predict_B, had pH values of 7.80-pCO2 = 749.12 ± 27.03 and 7.40-pCO2 = 321.37 ± 11.48 µatm, respectively. The experiment was preceded by 2 weeks of acclimation. After the acclimation, 20 juvenile black sea breams (Acanthopagrus schlegelii) of 2.72 ± 0.01 g were used per tank. This species has been selected mainly due to its very high resistance to diseases and environmental changes, assuming that a weaker fish resistance will also be susceptibly affected. In all tanks, the fish were fed with the same commercial diet. The seawater's physicochemical parameters were measured daily. Fish samples were subjected to physiological, histological, and biochemical analyses. Fish growth, feeding efficiency, protein efficiency ratio, and crude protein content were significantly decreased with a lower pH. Scanning electron microscopy revealed multiple atrophies of microvilli throughout the small intestine's brush border in samples from Predict_A and Predict_B. This significantly reduced nutrient absorption, resulting in significantly lower feed efficiency, lower fish growth, and lower meat quality. As a result of an elevated pCO2 in seawater, the fish eat more than normal but grow less than normal. Liver observation showed blood congestion, hemorrhage, necrosis, vacuolation of hepatocytes, and an increased number of Kupffer cells, which characterize liver damage. Transmission electron microscopy revealed an elongated and angular shape of the mitochondrion in the liver cell, with an abundance of peroxisomes, symptomatic of metabolic acidosis. [ABSTRACT FROM AUTHOR]

Acclimation responses of the red alga Gracilaria tenuistipitata var. liui collected on the northwest coast of Philippines were determined in laboratory setups and outdoor cultivation tanks in Haifa, Israel. Growth under laboratory conditions was influenced by all three variables studied, namely, temperature (20 or 30 °C), salinity (20, 30 or39‰) and seawater pH (6.5, 7.0, 8.0 or ≥ 9.0). In 250 mL flasks lacking pH control growth was influenced by temperature only at 20 ‰, whereas at 39 ‰, growth rates were similar at 20 or 30 °C. In 500 mL cylinders in which pH was controlled, growth rates were significantly different at a pH of 6.5 and 7.0 for all salinities, with maximal rates occurring in 39 ‰. At pH 8.0, and above, growth rates between salinities were similar and reduced to approximately 50% at a pH of 9.0 compared to rates at a pH of 6.5. Photosynthesis responses generally resembled growth responses both, in 250 mL and 500 mL cultures. In 40-L outdoor tanks, weekly growth and agar yields were apparently enhanced by increasing light intensities (up to full sunlight) and nutrient concentrations (up to 0.2 mM PO3 2- and 2.0 mM NH4 +), and rates averaged four times higher than rates determined in the smaller flask cultures. This study shows broad salinity tolerance of G. tenuistipitata var. liui and its ability to sustain growth rates that are among the highest measured for Gracilaria spp. in outdoor cultures. [ABSTRACT FROM AUTHOR]

Coral reef community composition, function, and resilience have been altered by natural and anthropogenic stressors. Future anthropogenic ocean and coastal acidification (together termed "acidification") may exacerbate this reef degradation. Accurately predicting reef resilience requires an understanding of not only direct impacts of acidification on marine organisms but also indirect effects on species interactions that influence community composition and reef ecosystem functions. In this 28-day experiment, we assessed the effect of acidification on coral–algal, coral–sponge, and algal–sponge interactions. We quantified growth of corals (Siderastrea radians), fleshy macroalgae (Dictyota spp.), and sponges (Pione lampa) that were exposed to local summer ambient (603 μatm) or elevated (1105 μatm) pCO2 seawater. These species are common to hard-bottom communities, including shallow reefs, in the Florida Keys. Each individual was maintained in isolation or paired with another organism. Coral growth (net calcification) was similar across seawater pCO2 and interaction treatments. Fleshy macroalgae had increased biomass when paired with a sponge but lost biomass when growing in isolation or paired with coral. Sponges grew more volumetrically in the elevated seawater pCO2 treatment (i.e., under acidification conditions). Although these results are limited in temporal and spatial scales due to the experimental design, they do lend support to the hypothesis that acidification may facilitate a shift towards increased sponge and macroalgae abundance by directly benefiting sponge growth which in turn may provide more dissolved inorganic nitrogen to macroalgae in the Florida Keys. [ABSTRACT FROM AUTHOR]

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 (pH spec – pH TA,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 CO 2 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 pH spec and pH TA,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. • Spectrophotometric and ISFET pH were compared in natural seawater over a large range of pH (7–8.5) and temperature (5–30°C) • Excellent agreement of better than 0.003 was observed at most temperatures and pH • pH dependent errors in pH spec can be rejected as the primary source of the discrepancy between pH spec and pH TA,DIC [ABSTRACT FROM AUTHOR]

Glass electrodes are commonly used to measure the pH of natural waters over various, sometimes wide, ranges of salinity (S). For such applications, the electrodes must be calibrated against solutions of known pH and salinity identical to those of the sample solutions. Well-characterized buffer solutions may be used for these calibrations, but if a wide range of salinity is to be encountered in the samples (e.g., as in estuarine transects), this approach is quite laborious. Previous work has demonstrated that for 28.5 < S < 36.1, pH electrodes can be efficiently calibrated spectrophotometrically in seawater because electrode intercept potential E 0 (a key calibration parameter) varies linearly with salinity over that range. The present work (a) characterizes pH electrode calibration parameters in seawater over a wider range of salinity (0.5 < S < 36) and (b) provides a simple and efficient method for creating and maintaining "river-to-sea" electrode calibrations over periods of months. Electrode calibration slope (g ') was found to be insensitive to salinity, as expected. The value of this parameter, measured at S > 5, was reliably consistent with theoretical expectations, such that repeat verification needs to be conducted only occasionally. Electrode intercept potential (E 0), in contrast, was found to depend substantially on salinity: approximately linearly for 5 ≤ S ≤ 36 and substantially nonlinearly for 0.5 ≤ S < 5. Ignoring this dependence of E 0 on S can lead to pH misestimates as large as 0.24, with the problem being most severe at lower salinities. Based on these observations, a method was developed by which the dependence of E 0 on S can be rapidly ascertained by simultaneously measuring pH (spectrophotometrically) and electromotive force (potentiometrically) in seawater that is serially diluted to produce the full range of salinities to be encountered in sampling. Because no acid titrations are required, a full river-to-sea calibration can be acquired in <3 h. With occasional (daily to weekly) one-point checks/corrections for electrode drift, this calibration is stable for weeks to months. • Calibration parameters for glass pH electrodes are highly nonlinear at salinities <5. • These nonlinearities can lead to pH measurement errors of 0.12 to 0.24 at S < 5. • A method is presented to calibrate pH electrodes over a river-to-sea range of S. • Such calibrations require <3 h. • These calibrations allow for quantitative electrode pH measurements over 0.5 < S < 36.1. [ABSTRACT FROM AUTHOR]

Impacts of the interactive effects of ocean acidification (OA) with other anthropogenic environmental stressors on marine biodiversity are receiving increasing attention in recent years. However, little is known about how organismal responses to OA may be influenced by common phenomena such as autotomy and sexual dimorphism. This study evaluated the long-term (120 days) combined effects of OA (pH 7.7), experimental cheliped amputation and sex on physiological stress (mortality, growth, number of molts, cheliped regeneration and startle response) and energy budget (lipid and calcium contents) in the intertidal sexually-dimorphic hermit crab Pagurus criniticornis. Crabs exposed to OA reduced survivorship (46%), molting frequency (36%) and lipid content (42%). Autotomised crabs and males molted more frequently (39% and 32%, respectively). Males presented higher regeneration (33%) and lower lipid content (24%). The few synergistic effects recorded did not indicate any clear pattern among treatments however, (1) a stronger reduction in lipid content was recorded in non-autotomised crabs exposed to low pH; (2) calcium content was higher in males than females only for autotomised crabs under control pH; and (3) autotomised females showed a proportionally slower activity recovery than autotomised males. Although our results suggest an effect of long-term exposure to low pH on the physiological stress and energy budget of Pagurus criniticornis , the physiological repertoire and plasticity associated with limb regeneration and the maintenance of dimorphism in secondary sexual characters may provide resilience to long-term exposure to OA. • First study to assess long-term combined effects of OA, autotomy and sex on crustaceans. • Crabs exposed to OA exhibited reduced survivorship, molting frequency and lipid content. • Males showed increased molting frequency and higher regeneration rate than females. • Interactive effects of pH, autotomy and sex were evidenced only for calcium content. • There are no evident synergy of autotomy and sex on the effects of OA on hermit crabs. [ABSTRACT FROM AUTHOR]