Variability In Carbonate Chemistry Research Articles

Ocean acidification and calcium carbonate saturation states in the coastal zone of the West Antarctic Peninsula

The polar oceans are particularly vulnerable to ocean acidification; the lowering of seawater pH and carbonate mineral saturation states due to uptake of atmospheric carbon dioxide (CO2). High spatial variability in surface water pH and saturation states (Ω) for two biologically-important calcium carbonate minerals calcite and aragonite was observed in Ryder Bay, in the coastal sea-ice zone of the West Antarctic Peninsula. Glacial meltwater and melting sea ice stratified the water column and facilitated the development of large phytoplankton blooms and subsequent strong uptake of atmospheric CO2 of up to 55 mmol m-2 day-1 during austral summer. Concurrent high pH (8.48) and calcium carbonate mineral supersaturation (Ωaragonite ~3.1) occurred in the meltwater-influenced surface ocean. Biologically-induced increases in calcium carbonate mineral saturation states counteracted any effects of carbonate ion dilution. Accumulation of CO2 through remineralisation of additional organic matter from productive coastal waters lowered the pH (7.84) and caused deep-water corrosivity (Ωaragonite ~0.9) in regions impacted by Circumpolar Deep Water. Episodic mixing events enabled CO2-rich subsurface water to become entrained into the surface and eroded seasonal stratification to lower surface water pH (8.21) and saturation states (Ωaragonite ~1.8) relative to all surface waters across Ryder Bay. Uptake of atmospheric CO2 of 28 mmol m-2 day-1 in regions of vertical mixing may enhance the susceptibility of the surface layer to future ocean acidification in dynamic coastal environments. Spatially-resolved studies are essential to elucidate the natural variability in carbonate chemistry in order to better understand and predict carbon cycling and the response of marine organisms to future ocean acidification in the Antarctic coastal zone.

A year in the life of a central California kelp forest: physical and biological insights into biogeochemical variability

Abstract. Kelp forests are among the world's most productive marine ecosystems, yet little is known about their biogeochemistry. This study presents a 14-month time series (July 2013–August 2014) of surface and benthic dissolved inorganic carbon and total alkalinity measurements, along with accompanying hydrographic measurements, from six locations within a central California kelp forest. We present ranges and patterns of variability in carbonate chemistry, including pH (7.70–8.33), pCO2 (172–952 µatm), and the aragonite saturation state, ΩAr (0.94–3.91). Surface-to-bottom gradients in CO2 system chemistry were as large as the spatial gradients throughout the bottom of the kelp forest. Dissolved inorganic carbon variability was the main driver of the observed CO2 system variability. The majority of spatial variability in the kelp forest can be explained by advection of cold, dense high-CO2 waters into the bottom of the kelp forest, with deeper sites experiencing high-CO2 conditions more frequently. Despite the strong imprint of advection on the biogeochemical variability of the kelp forest, surface waters were undersaturated with CO2 in the spring through fall, indicative of the strong role of photosynthesis on biogeochemical variability. We emphasize the importance of spatially distributed measurements for developing a process-based understanding of kelp forest ecosystem function in a changing climate.

Physiological plasticity and local adaptation to elevated pCO2 in calcareous algae: an ontogenetic and geographic approach.

To project how ocean acidification will impact biological communities in the future, it is critical to understand the potential for local adaptation and the physiological plasticity of marine organisms throughout their entire life cycle, as some stages may be more vulnerable than others. Coralline algae are ecosystem engineers that play significant functional roles in oceans worldwide and are considered vulnerable to ocean acidification. Using different stages of coralline algae, we tested the hypothesis that populations living in environments with higher environmental variability and exposed to higher levels of pCO 2 would be less affected by high pCO 2 than populations from a more stable environment experiencing lower levels of pCO 2. Our results show that spores are less sensitive to elevated pCO 2 than adults. Spore growth and mortality were not affected by pCO 2 level; however, elevated pCO 2 negatively impacted the physiology and growth rates of adults, with stronger effects in populations that experienced both lower levels of pCO 2 and lower variability in carbonate chemistry, suggesting local adaptation. Differences in physiological plasticity and the potential for adaptation could have important implications for the ecological and evolutionary responses of coralline algae to future environmental changes.

Interannual stability of organic to inorganic carbon production on a coral atoll

AbstractOcean acidification has the potential to adversely affect marine calcifying organisms, with substantial ocean ecosystem impacts projected over the 21st century. Characterizing the in situ sensitivity of calcifying ecosystems to natural variability in carbonate chemistry may improve our understanding of the long‐term impacts of ocean acidification. We explore the potential for intensive temporal sampling to isolate the influence of carbonate chemistry on community calcification rates of a coral reef and compare the ratio of organic to inorganic carbon production to previous studies at the same location. Even with intensive temporal sampling, community calcification displays only a weak dependence on carbonate chemistry variability. However, across three years of sampling, the ratio of organic to inorganic carbon production is highly consistent. Although further work is required to quantify the spatial variability associated with such ratios, this suggests that these measurements have the potential to indicate the response of coral reefs to ongoing disturbance, ocean acidification, and climate change.

Physical and biogeochemical controls on the variability in surface pH and calcium carbonate saturation states in the Atlantic sectors of the Arctic and Southern Oceans

Polar oceans are particularly vulnerable to ocean acidification due to their low temperatures and reduced buffering capacity, and are expected to experience extensive low pH conditions and reduced carbonate mineral saturations states (Ω) in the near future. However, the impact of anthropogenic CO2 on pH and Ω will vary regionally between and across the Arctic and Southern Oceans. Here we investigate the carbonate chemistry in the Atlantic sector of two polar oceans, the Nordic Seas and Barents Sea in the Arctic Ocean, and the Scotia and Weddell Seas in the Southern Ocean, to determine the physical and biogeochemical processes that control surface pH and Ω. High-resolution observations showed large gradients in surface pH (0.10–0.30) and aragonite saturation state (Ωar) (0.2–1.0) over small spatial scales, and these were particularly strong in sea-ice covered areas (up to 0.45 in pH and 2.0 in Ωar). In the Arctic, sea-ice melt facilitated bloom initiation in light-limited and iron replete (dFe>0.2nM) regions, such as the Fram Strait, resulting in high pH (8.45) and Ωar (3.0) along the sea-ice edge. In contrast, accumulation of dissolved inorganic carbon derived from organic carbon mineralisation under the ice resulted in low pH (8.05) and Ωar (1.1) in areas where thick ice persisted. In the Southern Ocean, sea-ice retreat resulted in bloom formation only where terrestrial inputs supplied sufficient iron (dFe>0.2nM), such as in the vicinity of the South Sandwich Islands where enhanced pH (8.3) and Ωar (2.3) were primarily due to biological production. In contrast, in the adjacent Weddell Sea, weak biological uptake of CO2 due to low iron concentrations (dFe<0.2nM) resulted in low pH (8.1) and Ωar (1.6). The large spatial variability in both polar oceans highlights the need for spatially resolved surface data of carbonate chemistry variables but also nutrients (including iron) in order to accurately elucidate the large gradients experienced by marine organisms and to understand their response to increased CO2 in the future.

Experimental determination of factors controlling U/Ca of aragonite precipitated from seawater: Implications for interpreting coral skeleton

The U/Ca ratio of aragonite coral skeleton exhibits coherent patterns of seasonal and interannual variability. In field-sampled corals and those grown in controlled culture experiments, strong correlations have been found between coral skeleton U/Ca and water temperature, pH, carbonate ion concentration, and salinity. However, the mechanism(s) underlying these different correlations remain unclear. We performed abiogenic precipitation experiments designed to evaluate the sensitivity of U partitioning between aragonite and seawater to temperature, pH, and the concentration of carbonate ion in seawater. Aragonite was precipitated from seawater by addition of carbonate alkalinity at rates set to maintain stable carbonate chemistry during precipitation. Experiments were conducted at 20–40°C, with pH 7.8–9.0 and carbonate ion concentrations of 600–2600μmolkg−1. U/Ca ratios of the bulk precipitate and fluid were determined by inductively coupled plasma mass spectrometry. Our results show that the U/Ca ratio of aragonite precipitated from seawater decreases with increasing carbonate ion concentration, and is independent of pH and temperature. We use these results as a framework to interpret the skeletal composition of coral aragonite precipitated from a calcifying fluid that is semi-isolated from the external seawater environment. Accordingly, coral U/Ca ratios are consistent with calcifying fluid carbonate ion concentrations that are several times greater than those of ambient seawater. Correlations between coral U/Ca ratios and seawater temperature, carbonate chemistry, and other environmental variables arise indirectly, via the impacts of these variables on the carbonate ion concentration of the coral calcifying fluid.

Is coccolithophore distribution in the Mediterranean Sea related to seawater carbonate chemistry?

Abstract. The Mediterranean Sea is considered a "hot spot" for climate change, being characterized by oligotrophic to ultra-oligotrophic waters and rapidly increasing seasurface temperature and changing carbonate chemistry. Coccolithophores are considered a dominant phytoplankton group in these waters. As marine calcifying organisms they are expected to respond to the ongoing changes in seawater carbonate chemistry. We provide here a description of the springtime coccolithophore distribution in the Mediterranean Sea and relate this to a broad set of in situ-measured environmental variables. Samples were taken during the R/V Meteor (M84/3) oceanographic cruise in April 2011, between 0 and 100 m water depth from 28 stations. Total diatom and silicoflagellate cell concentrations are also presented. Our results highlight the importance of seawater carbonate chemistry, especially [CO32−] but also [PO43−] in unraveling the distribution of heterococcolithophores, the most abundant coccolithophore life phase. Holo- and heterococcolithophores respond differently to environmental factors. For instance, changes in heterococcolithophore assemblages were best linked to the combination of [CO32−], pH, and salinity (ρ = 0.57), although salinity might be not functionally related to coccolithophore assemblage distribution. Holococcolithophores, on the other hand, showed higher abundances and species diversity in oligotrophic areas (best fit, ρ = 0.32 for nutrients), thriving in nutrient-depleted waters. Clustering of heterococcolithophores revealed three groups of species sharing more than 65% similarities. These clusters could be assigned to the eastern and western basins and deeper layers (below 50 m), respectively. In addition, the species Gephyrocapsa oceanica, G. muellerae, and Emiliania huxleyi morphotype B/C are spatially distributed together and trace the influx of Atlantic waters into the Mediterranean Sea. The results of the present work emphasize the importance of considering holo- and heterococcolithophores separately when analyzing changes in species assemblages and diversity. Our findings suggest that coccolithophores are a main phytoplankton group in the entire Mediterranean Sea and can dominate over siliceous phytoplankton. They have life stages that are expected to respond differently to the variability in seawater carbonate chemistry and nutrient concentrations.

Interpretation and design of ocean acidification experiments in upwelling systems in the context of carbonate chemistry co-variation with temperature and oxygen

AbstractCoastal upwelling regimes are some of the most productive ecosystems in the ocean but are also among the most vulnerable to ocean acidification (OA) due to naturally high background concentrations of CO2. Yet our ability to predict how these ecosystems will respond to additional CO2 resulting from anthropogenic emissions is poor. To help address this uncertainty, researchers perform manipulative experiments where biological responses are evaluated across different CO2 partial pressure (pCO2) levels. In upwelling systems, however, contemporary carbonate chemistry variability remains only partly characterized and patterns of co-variation with other biologically important variables such as temperature and oxygen are just beginning to be explored in the context of OA experimental design. If co-variation among variables is prevalent, researchers risk performing OA experiments with control conditions that are not experienced by the focal species, potentially diminishing the ecological relevance of the experiment. Here, we synthesized a large carbonate chemistry dataset that consists of carbonate chemistry, temperature, and oxygen measurements from multiple moorings and ship-based sampling campaigns from the California Current Ecosystem (CCE), and includes fjord and tidal estuaries and open coastal waters. We evaluated patterns of pCO2 variability and highlight important co-variation between pCO2, temperature, and oxygen. We subsequently compared environmental pCO2–temperature measurements with conditions maintained in OA experiments that used organisms from the CCE. By drawing such comparisons, researchers can gain insight into the ecological relevance of previously published OA experiments, but also identify species or life history stages that may already be influenced by contemporary carbonate chemistry conditions. We illustrate the implications co-variation among environmental variables can have for the interpretation of OA experimental results and suggest an approach for designing experiments with pCO2 levels that better reflect OA hypotheses while simultaneously recognizing natural co-variation with other biologically relevant variables.

Relative roles of endolithic algae and carbonate chemistry variability in the skeletal dissolution of crustose coralline algae

Abstract. The susceptibility of crustose coralline algae (CCA) skeletons to dissolution is predicted to increase as oceans warm and acidify. Skeletal dissolution is caused by bioerosion from endolithic microorganisms and by chemical processes associated with undersaturation of carbonate minerals in seawater. Yet, the relative contribution of algal microborers and seawater carbonate chemistry to the dissolution of organisms that cement reefs under projected pCO2 and temperature (pCO2-T) scenarios have not been quantified. We exposed CCA skeletons (Porolithon onkodes) to four pCO2-T treatments (pre-industrial, present-day, SRES-B1 "reduced" pCO2, and SRES-A1FI "business-as-usual" pCO2 emission scenarios) under natural light cycles vs. constant dark conditions for 8 weeks. Dissolution rates of skeletons without photo-endoliths were dramatically higher (200%) than those colonized by endolithic algae across all pCO2-T scenarios. This suggests that daytime photosynthesis by microborers counteract dissolution by reduced saturation states resulting in lower net erosion rates over day–night cycles. Regardless of the presence or absence of phototrophic microborers, skeletal dissolution increased significantly under the spring A1FI "business-as-usual" scenario, confirming the CCA sensitivity to future oceans. Projected ocean acidity and temperature may significantly disturb the stability of reef frameworks cemented by CCA, but surficial substrates harbouring photosynthetic microborers will be less impacted than those without algal endoliths.

Intercomparison of carbonate chemistry measurements on a cruise in northwestern European shelf seas

Abstract. Four carbonate system variables were measured in surface waters during a cruise aimed at investigating ocean acidification impacts traversing northwestern European shelf seas in the summer of 2011. High-resolution surface water data were collected for partial pressure of carbon dioxide (pCO2; using two independent instruments) and pH using the total pH scale (pHT), in addition to discrete measurements of total alkalinity and dissolved inorganic carbon. We thus overdetermined the carbonate system (four measured variables, two degrees of freedom), which allowed us to evaluate the level of agreement between the variables on a cruise whose main aim was not intercomparison, and thus where conditions were more representative of normal working conditions. Calculations of carbonate system variables from other measurements generally compared well with direct observations of the same variables (Pearson's correlation coefficient always greater than or equal to 0.94; mean residuals were similar to the respective accuracies of the measurements). We therefore conclude that four of the independent data sets of carbonate chemistry variables were of high quality. A diurnal cycle with a maximum amplitude of 41 μatm was observed in the difference between the pCO2 values obtained by the two independent analytical pCO2 systems, and this was partly attributed to irregular seawater flows to the equilibrator and partly to biological activity inside the seawater supply and one of the equilibrators. We discuss how these issues can be addressed to improve carbonate chemistry data quality on future research cruises.

Climatological distributions of pH, pCO2, total CO2, alkalinity, and CaCO3 saturation in the global surface ocean, and temporal changes at selected locations

Climatological mean monthly distributions of pH in the total H+ scale, total CO2 concentration (TCO2), and the degree of CaCO3 saturation for the global surface ocean waters (excluding coastal areas) are calculated using a data set for pCO2, alkalinity and nutrient concentrations in surface waters (depths <50m), which is built upon the GLODAP, CARINA and LDEO databases. The mutual consistency among these measured parameters is demonstrated using the inorganic carbon chemistry model with the dissociation constants for carbonic acid by Lueker et al. (2000) and for boric acid by Dickson (1990). Linear potential alkalinity-salinity relationships are established for 24 regions of the global ocean. The mean monthly distributions of pH and carbon chemistry parameters for the reference year 2005 are computed using the climatological mean monthly pCO2 data adjusted to a reference year 2005 and the alkalinity estimated from the potential alkalinity-salinity relationships. The equatorial zone (4°N-4°S) of the Pacific is excluded from the analysis because of the large interannual changes associated with ENSO events. The pH thus calculated ranges from 7.9 to 8.2. Lower values are located in the upwelling regions in the tropical Pacific and in the Arabian and Bering Seas; higher values are found in the subpolar and polar waters during the spring-summer months of intense photosynthetic production. The vast areas of subtropical oceans have seasonally varying pH values ranging from 8.05 during warmer months to 8.15 during colder months. The warm tropical and subtropical waters are supersaturated by a factor of as much as 4.2 with respect to aragonite and 6.3 for calcite, whereas the cold subpolar and polar waters are supersaturated by 1.2 for aragonite and 2.0 for calcite because of the lower pH values resulting from greater TCO2 concentrations. In the western Arctic Ocean, aragonite undersaturation is observed. The time-series data from the Bermuda (BATS), Hawaii (HOT), Canary (ESTOC) and the Drake Passage show that pH has been declining at a mean rate of about -0.02 pH per decade, and that pCO2 has been increasing at about 19 μatm per decade tracking the atmospheric pCO2 increase rate. This suggests that the ocean acidification is caused primarily by the uptake of atmospheric CO2. The relative importance of the four environmental drivers (temperature, salinity, alkalinity and total CO2 concentration) controlling the seasonal variability of carbonate chemistry at these sites is quantitatively assessed. The ocean carbon chemistry is governed sensitively by the TA/TCO2 ratio, and the rate of change in TA is equally important for the future ocean environment as is the TCO2 in ocean waters increases in the future.

The role of ocean acidification in &amp;lt;i&amp;gt;Emiliania huxleyi&amp;lt;/i&amp;gt; coccolith thinning in the Mediterranean Sea

Abstract. Ocean acidification is a result of the uptake of anthropogenic CO2 from the atmosphere into the ocean and has been identified as a major environmental and economic threat. The release of several thousands of petagrams of carbon over a few hundred years will have an overwhelming effect on surface ocean carbon reservoirs. The recorded and anticipated changes in seawater carbonate chemistry will presumably affect global oceanic carbonate production. Coccolithophores as the primary calcifying phytoplankton group, and especially Emiliania huxleyi as the most abundant species have shown a reduction of calcification at increased CO2 concentrations for the majority of strains tested in culture experiments. A reduction of calcification is associated with a decrease in coccolith weight. However, the effect in monoclonal cultures is relatively small compared to the strong variability displayed in natural E. huxleyi communities, as these are a mix of genetically and sometimes morphologically distinct types. Average coccolith weight is likely influenced by the variability in seawater carbonate chemistry in different parts of the world's oceans and on glacial/interglacial time scales due to both physiological effects and morphotype selectivity. An effect of the ongoing ocean acidification on E. huxleyi calcification has so far not been documented in situ. Here, we analyze E. huxleyi coccolith weight from the NW Mediterranean Sea in a 12-year sediment trap series, and surface sediment and sediment core samples using an automated recognition and analyzing software. Our findings clearly show (1) a continuous decrease in the average coccolith weight of E. huxleyi from 1993 to 2005, reaching levels below pre-industrial (Holocene) and industrial (20th century) values recorded in the sedimentary record and (2) seasonal variability in coccolith weight that is linked to the coccolithophore productivity. The observed long-term decrease in coccolith weight is most likely a result of the changes in the surface ocean carbonate system. Our results provide the first indications of an in situ impact of ocean acidification on coccolithophore weight in a natural E. huxleyi population, even in the highly alkaline Mediterranean Sea.

The interacting effects of photosynthesis, calcification and water circulation on carbon chemistry variability on a coral reef flat: A modelling study

The diurnal fluctuations in seawater carbon chemistry that occur at sites within a coral reef system are due to water circulation, air-sea heat and gas exchange, and biogeochemical processes. The daily changes in dissolved carbon ion speciation and pHT on reefs can be larger than the century-scale shifts predicted for open ocean waters under climate change scenarios. We implement a 167m resolution 3D hydrodynamic model of a coral reef (Heron Island reef, southern Great Barrier Reef, Australia) and couple it to a carbon biogeochemistry model. The model is forced by benthic fluxes calculated using a detailed habitat map and light and habitat-dependent parameterisations of calcification/photosynthesis developed from flume studies on Heron Island. During a two month simulation the model is able to reproduce the observed variability in the water temperature at 8 locations within the reef, demonstrating an ability of the model to capture the circulation. The simulation shows that the dominant processes driving the variability in carbonate chemistry at a location on the reef are the location of the different benthic communities and the path the water has taken to arrive at that location. A spatially-resolved age tracer indicates that the residence time of water over the reef varied between 16 and 60h, depending on tides, winds and location. The longer transit times over the reef reduced the aragonite saturation state, Ωa, in the overlying water to as low as 2. In the model simulation, the reef ecosystem reduces Ωa at a rate of 0.018 per hour on the reef. A scenario in which we removed the non-calcifying benthic microalgae from the reef showed a reduction in the Ωa in some regions from 5 to 2.5, and an average reduction of the coral calcification by 15%. This demonstrates the importance of processes that can alter the photosynthesis/respiration and calcification/dissolution balance when considering climate change impacts due to ocean acidification on corals at the reef scale.

Seasonal Carbonate Chemistry Covariation with Temperature, Oxygen, and Salinity in a Fjord Estuary: Implications for the Design of Ocean Acidification Experiments

Carbonate chemistry variability is often poorly characterized in coastal regions and patterns of covariation with other biologically important variables such as temperature, oxygen concentration, and salinity are rarely evaluated. This absence of information hampers the design and interpretation of ocean acidification experiments that aim to characterize biological responses to future pCO2 levels relative to contemporary conditions. Here, we analyzed a large carbonate chemistry data set from Puget Sound, a fjord estuary on the U.S. west coast, and included measurements from three seasons (winter, summer, and fall). pCO2 exceeded the 2008–2011 mean atmospheric level (392 µatm) at all depths and seasons sampled except for the near-surface waters (< 10 m) in the summer. Further, undersaturated conditions with respect to the biogenic carbonate mineral aragonite were widespread (Ωar<1). We show that pCO2 values were relatively uniform throughout the water column and across regions in winter, enriched in subsurface waters in summer, and in the fall some values exceeded 2500 µatm in near-surface waters. Carbonate chemistry covaried to differing levels with temperature and oxygen depending primarily on season and secondarily on region. Salinity, which varied little (27 to 31), was weakly correlated with carbonate chemistry. We illustrate potential high-frequency changes in carbonate chemistry, temperature, and oxygen conditions experienced simultaneously by organisms in Puget Sound that undergo diel vertical migrations under present-day conditions. We used simple calculations to estimate future pCO2 and Ωar values experienced by diel vertical migrators based on an increase in atmospheric CO2. Given the potential for non-linear interactions between pCO2 and other abiotic variables on physiological and ecological processes, our results provide a basis for identifying control conditions in ocean acidification experiments for this region, but also highlight the wide range of carbonate chemistry conditions organisms may currently experience in this and similar coastal ecosystems.

Seasonal variability in carbonate chemistry and air–sea CO2 fluxes in the southern Great Barrier Reef

There is presently little known about temporal variability in CO2 and carbonate chemistry (pH and aragonite saturation state (Ωarag)) in the Great Barrier Reef (GBR) region. In this study we investigated both the seasonal variability of the carbonate system and the air–sea CO2 fluxes in waters offshore of Lady Elliot Island, southern GBR, between the austral spring of 2009 and winter 2010. During winter, the partial pressure of CO2 (pCO2) was found to be the lowest (343μatm), rising by 61μatm to nearly 404μatm during summer. Much of the variance in pCO2 and pH could be described by sea surface temperature (SST) and its thermodynamic effect on CO2. Despite the relatively large seasonal pCO2 signal (~60 μatm), we found little seasonal variability in Ωarag, which maintained a level of 3.6 throughout the seasons. Seasonal changes in dissolved inorganic carbon (DIC) and total alkalinity (TA), were found to offset each other during the seasons, thereby resulting in little seasonal variability to Ωarag. These results suggest that within southern GBR waters, future ocean acidification changes can be accurately predicted using various high-CO2 future scenarios without the need to account for seasonal variability that has been found to modulate the timing or onset of future oceanic acidification elsewhere in the ocean. For CO2, we found these waters to be up to 50μatm lower than the atmosphere for nine months of the year, implying an annual CO2 sink. Using the robust relationship between SST and pCO2, we calculate the region to be a weak sink for CO2 (flux of −665mmolCm−2y−1). If we extrapolate our results to the wider southern GBR south of 20°S, it would imply a net CO2 sink of ~1TgCy−1.

Anthropogenic changes to seawater buffer capacity combined with natural reef metabolism induce extreme future coral reef CO2 conditions

Ocean acidification, via an anthropogenic increase in seawater carbon dioxide (CO2 ), is potentially a major threat to coral reefs and other marine ecosystems. However, our understanding of how natural short-term diurnal CO2 variability in coral reefs influences longer term anthropogenic ocean acidification remains unclear. Here, we combine observed natural carbonate chemistry variability with future carbonate chemistry predictions for a coral reef flat in the Great Barrier Reef based on the RCP8.5 CO2 emissions scenario. Rather than observing a linear increase in reef flat partial pressure of CO2 (pCO2 ) in concert with rising atmospheric concentrations, the inclusion of in situ diurnal variability results in a highly nonlinear threefold amplification of the pCO2 signal by the end of the century. This significant nonlinear amplification of diurnal pCO2 variability occurs as a result of combining natural diurnal biological CO2 metabolism with long-term decreases in seawater buffer capacity, which occurs via increasing anthropogenic CO2 absorption by the ocean. Under the same benthic community composition, the amplification in the variability in pCO2 is likely to lead to exposure to mean maximum daily pCO2 levels of ca. 2100μatm, with corrosive conditions with respect to aragonite by end-century at our study site. Minimum pCO2 levels will become lower relative to the mean offshore value (ca. threefold increase in the difference between offshore and minimum reef flat pCO2 ) by end-century, leading to a further increase in the pCO2 range that organisms are exposed to. The biological consequences of short-term exposure to these extreme CO2 conditions, coupled with elevated long-term mean CO2 conditions are currently unknown and future laboratory experiments will need to incorporate natural variability to test this. The amplification of pCO2 that we describe here is not unique to our study location, but will occur in all shallow coastal environments where high biological productivity drives large natural variability in carbonate chemistry.

Ocean Acidification Refugia of the Florida Reef Tract

Ocean acidification (OA) is expected to reduce the calcification rates of marine organisms, yet we have little understanding of how OA will manifest within dynamic, real-world systems. Natural CO2, alkalinity, and salinity gradients can significantly alter local carbonate chemistry, and thereby create a range of susceptibility for different ecosystems to OA. As such, there is a need to characterize this natural variability of seawater carbonate chemistry, especially within coastal ecosystems. Since 2009, carbonate chemistry data have been collected on the Florida Reef Tract (FRT). During periods of heightened productivity, there is a net uptake of total CO2 (TCO2) which increases aragonite saturation state (Ωarag) values on inshore patch reefs of the upper FRT. These waters can exhibit greater Ωarag than what has been modeled for the tropical surface ocean during preindustrial times, with mean (± std. error) Ωarag-values in spring = 4.69 (±0.101). Conversely, Ωarag-values on offshore reefs generally represent oceanic carbonate chemistries consistent with present day tropical surface ocean conditions. This gradient is opposite from what has been reported for other reef environments. We hypothesize this pattern is caused by the photosynthetic uptake of TCO2 mainly by seagrasses and, to a lesser extent, macroalgae in the inshore waters of the FRT. These inshore reef habitats are therefore potential acidification refugia that are defined not only in a spatial sense, but also in time; coinciding with seasonal productivity dynamics. Coral reefs located within or immediately downstream of seagrass beds may find refuge from OA.

Diurnal changes in seawater carbonate chemistry speciation at increasing atmospheric carbon dioxide

Natural variability in seawater pH and associated carbonate chemistry parameters is in part driven by biological activities such as photosynthesis and respiration. The amplitude of these variations is expected to increase with increasing seawater carbon dioxide (CO2) concentrations in the future, because of simultaneously decreasing buffer capacity. Here, we address this experimentally during a diurnal cycle in a mesocosm CO2 perturbation study. We show that for about the same amount of dissolved inorganic carbon (DIC) utilized in net community production diel variability in proton (H+) and CO2 concentrations was almost three times higher at CO2 levels of about 675 ± 65 in comparison with levels of 310 ± 30 μatm. With a simple model, adequately simulating our measurements, we visualize carbonate chemistry variability expected for different oceanic regions with relatively low or high net community production. Since enhanced diurnal variability in CO2 and proton concentration may require stronger cellular regulation in phytoplankton to maintain respective gradients, the ability to adjust may differ between communities adapted to low in comparison with high natural variability.

Impacts of ocean acidification in naturally variable coral reef flat ecosystems

Ocean acidification leads to changes in marine carbonate chemistry that are predicted to cause a decline in future coral reef calcification. Several laboratory and mesocosm experiments have described calcification responses of species and communities to increasing CO2. The few in situ studies on natural coral reefs that have been carried out to date have shown a direct relationship between aragonite saturation state (Ωarag) and net community calcification (Gnet). However, these studies have been performed over a limited range of Ωarag values, where extrapolation outside the observational range is required to predict future changes in coral reef calcification. We measured extreme diurnal variability in carbonate chemistry within a reef flat in the southern Great Barrier Reef, Australia. Ωarag varied between 1.1 and 6.5, thus exceeding the magnitude of change expected this century in open ocean subtropical/tropical waters. The observed variability comes about through biological activity on the reef, where changes to the carbonate chemistry are enhanced at low tide when reef flat waters are isolated from open ocean water. We define a relationship between net community calcification and Ωarag, using our in situ measurements. We find net community calcification to be linearly related to Ωarag, while temperature and nutrients had no significant effect on Gnet. Using our relationship between Gnet and Ωarag, we predict that net community calcification will decline by 55% of its preindustrial value by the end of the century. It is not known at this stage whether exposure to large variability in carbonate chemistry will make reef flat organisms more or less vulnerable to the non‐calcifying physiological effects of increasing ocean CO2 and future laboratory studies will need to incorporate this natural variability to address this question.

Potential impacts of climate change on Northeast Pacific marine foodwebs and fisheries

Abstract Ainsworth, C. H., Samhouri, J. F., Busch, D. S., Cheung, W. W. L., Dunne, J., and Okey, T. A. 2011. Potential impacts of climate change on Northeast Pacific marine foodwebs and fisheries. – ICES Journal of Marine Science, 68: 1217–1229. Although there has been considerable research on the impacts of individual changes in water temperature, carbonate chemistry, and other variables on species, cumulative impacts of these effects have rarely been studied. Here, we simulate changes in (i) primary productivity, (ii) species range shifts, (iii) zooplankton community size structure, (iv) ocean acidification, and (v) ocean deoxygenation both individually and together using five Ecopath with Ecosim models of the northeast Pacific Ocean. We used a standardized method to represent climate effects that relied on time-series forcing functions: annual multipliers of species productivity. We focused on changes in fisheries landings, biomass, and ecosystem characteristics (diversity and trophic indices). Fisheries landings generally declined in response to cumulative effects and often to a greater degree than would have been predicted based on individual climate effects, indicating possible synergies. Total biomass of fished and unfished functional groups displayed a decline, though unfished groups were affected less negatively. Some functional groups (e.g. pelagic and demersal invertebrates) were predicted to respond favourably under cumulative effects in some regions. The challenge of predicting climate change impacts must be met if we are to adapt and manage rapidly changing marine ecosystems in the 21st century.