Shell Condition and Survival of Puget Sound Pteropods Are Impaired by Ocean Acidification Conditions

We tested whether the thecosome pteropod Limacina helicina from Puget Sound, an urbanized estuary in the northwest continental US, experiences shell dissolution and altered mortality rates when exposed to the high CO₂, low aragonite saturation state (Ω_a) conditions that occur in Puget Sound and the northeast Pacific Ocean. Five, week-long experiments were conducted in which we incubated pteropods collected from Puget Sound in four carbon chemistry conditions: current summer surface (∼460–500 µatm CO₂, Ω_a≈1.59), current deep water or surface conditions during upwelling (∼760 and ∼1600–1700 µatm CO₂, Ω_a≈1.17 and 0.56), and future deep water or surface conditions during upwelling (∼2800–3400 µatm CO₂, Ω_a≈0.28). We measured shell condition using a scoring regime of five shell characteristics that capture different aspects of shell dissolution. We characterized carbon chemistry conditions in statistical analyses with Ω_a, and conducted analyses considering Ω_a both as a continuous dataset and as discrete treatments. Shell dissolution increased linearly as aragonite saturation state decreased. Discrete treatment comparisons indicate that shell dissolution was greater in undersaturated treatments compared to oversaturated treatments. Survival increased linearly with aragonite saturation state, though discrete treatment comparisons indicated that survival was similar in all but the lowest saturation state treatment. These results indicate that, under starvation conditions, pteropod survival may not be greatly affected by current and expected near-future aragonite saturation state in the NE Pacific, but shell dissolution may. Given that subsurface waters in Puget Sound’s main basin are undersaturated with respect to aragonite in the winter and can be undersaturated in the summer, the condition and persistence of the species in this estuary warrants further study.     

Limacina helicina shell dissolution as an indicator of declining habitat suitability owing to ocean acidification in the California Current Ecosystem

Few studies to date have demonstrated widespread biological impacts of ocean acidification (OA) under conditions currently found in the natural environment. From a combined survey of physical and chemical water properties and biological sampling along the Washington–Oregon–California coast in August 2011, we show that large portions of the shelf waters are corrosive to pteropods in the natural environment. We show a strong positive correlation between the proportion of pteropod individuals with severe shell dissolution damage and the percentage of undersaturated water in the top 100 m with respect to aragonite. We found 53% of onshore individuals and 24% of offshore individuals on average to have severe dissolution damage. Relative to pre-industrial CO₂ concentrations, the extent of undersaturated waters in the top 100 m of the water column has increased over sixfold along the California Current Ecosystem (CCE). We estimate that the incidence of severe pteropod shell dissolution owing to anthropogenic OA has doubled in near shore habitats since pre-industrial conditions across this region and is on track to triple by 2050. These results demonstrate that habitat suitability for pteropods in the coastal CCE is declining. The observed impacts represent a baseline for future observations towards understanding broader scale OA effects.     

Impact of aragonite saturation state changes on migratory pteropods

Thecosome pteropods play a key role in the food web of various marine ecosystems and they calcify, secreting the unstable CaCO(3) mineral aragonite to form their shell material. Here, we have estimated the effect of ocean acidification on pteropod calcification by exploiting empirical relationships between their gross calcification rates (CaCO(3) precipitation) and aragonite saturation state Ω(a), combined with model projections of future Ω(a). These were corrected for modern model-data bias and taken over the depth range where pteropods are observed to migrate vertically. Results indicate large reductions in gross calcification at temperate and high latitudes. Over much of the Arctic, the pteropod Limacina helicina will become unable to precipitate CaCO(3) by the end of the century under the IPCC SRES A2 scenario. These results emphasize concerns over the future of shelled pteropods, particularly L. helicina in high latitudes. Shell-less L. helicina are not known to have ever existed nor would we expect them to survive. Declines of pteropod populations could drive dramatic ecological changes in the various pelagic ecosystems in which they play a critical role.     

Near‐future pH conditions severely impact calcification,metabolism and the nervous system in the pteropod Heliconoides inflatus

Shelled pteropods play key roles in the global carbon cycle and food webs of various ecosystems. Their thin external shell is sensitive to small changes in pH, and shell dissolution has already been observed in areas where aragonite saturation state is ~1. A decline in pteropod abundance has the potential to disrupt trophic networks and directly impact commercial fisheries. Therefore, it is crucial to understand how pteropods will be affected by global environmental change, particularly ocean acidification. In this study, physiological and molecular approaches were used to investigate the response of the Mediterranean pteropod, Heliconoides inflatus, to pH values projected for 2100 under a moderate emissions trajectory (RCP6.0). Pteropods were subjected to pH_T 7.9 for 3 days, and gene expression levels, calcification and respiration rates were measured relative to pH_T 8.1 controls. Gross calcification decreased markedly under low pH conditions, while genes potentially involved in calcification were up‐regulated, reflecting the inability of pteropods to maintain calcification rates. Gene expression data imply that under low pH conditions, both metabolic processes and protein synthesis may be compromised, while genes involved in acid–base regulation were up‐regulated. A large number of genes related to nervous system structure and function were also up‐regulated in the low pH treatment, including a GABA_A receptor subunit. This observation is particularly interesting because GABA_A receptor disturbances, leading to altered behavior, have been documented in several other marine animals after exposure to elevated CO₂. The up‐regulation of many genes involved in nervous system function suggests that exposure to low pH could have major effects on pteropod behavior. This study illustrates the power of combining physiological and molecular approaches. It also reveals the importance of behavioral analyses in studies aimed at understanding the impacts of low pH on marine animals.     

Interannual pteropod variability in sediment traps deployed above and below the aragonite saturation horizon in the Sub-Antarctic Southern Ocean

Anthropogenic inputs of CO₂ are altering ocean chemistry and may alter the role of marine calcifiers in ocean ecosystems. Laboratory research and ocean models suggest calcifiers in polar waters are especially at risk, particularly pteropods: pelagic aragonite-shelled molluscs. However, baseline data for natural populations of pteropods are limited, especially for polar and sub-polar waters. In order to establish baseline data on diversity, preservation state and shell flux of in situ populations of Sub-Antarctic Southern Ocean pteropods, we deployed sediment traps above (1,000 m) and below (2,000 m) the aragonite saturation horizon (ASH) (currently at 1,200 m) from 1997 to 2006 at 47°S, 142°E. We identified seven pteropod taxa. We applied a shell opacity index to each shell collected and found 50% of shells collected above the ASH to be in pristine condition but only 3% of the shells collected below the ASH showed such a high degree of preservation. We estimated pteropod shell mass fluxes for the region (0.17–4.99 mg m⁻² day⁻¹), and we identified significant reductions in shell flux for Limacina helicina antarctica forma rangi and Clio recurva to the trap series above the ASH and for Limacina helicina antarctica forma rangi and Limacina helicina antarctica forma antarctica to the trap series below the ASH over the interval 1997–2006. Our data establish a temporal and vertical snapshot of the current Sub-Antarctic pelagic pteropod community and provide a baseline against which to monitor Southern Ocean pteropods responses, if any, to changing ocean conditions projected for the region in the coming decades.     

Description and quantification of pteropod shell dissolution: a sensitive bioindicator of ocean acidification

Anthropogenic ocean acidification is likely to have negative effects on marine calcifying organisms, such as shelled pteropods, by promoting dissolution of aragonite shells. Study of shell dissolution requires an accurate and sensitive method for assessing shell damage. Shell dissolution was induced through incubations in CO₂‐enriched seawater for 4 and 14 days. We describe a procedure that allows the level of dissolution to be assessed and classified into three main types: Type I with partial dissolution of the prismatic layer; Type II with exposure of underlying crossed‐lamellar layer, and Type III, where crossed‐lamellar layer shows signs of dissolution. Levels of dissolution showed a good correspondence to the incubation conditions, with the most severe damage found in specimens held for 14 days in undersaturated condition (Ω ~ 0.8). This methodology enables the response of small pelagic calcifiers to acidified conditions to be detected at an early stage, thus making pteropods a valuable bioindicator of future ocean acidification.     

Microstructural shell strength of the Subantarctic pteropod <Emphasis Type="Italic">Limacina helicina antarctica</Emphasis>

Anthropogenic inputs of CO₂ are changing ocean chemistry and will likely affect calcifying marine organisms, particularly aragonite producers such as pteropods. This work seeks to set a benchmark analysis of pteropod shell properties and variability using nanoindentation and electron microscopy to measure the structural and mechanical properties of Subantarctic pteropod shells (Limacina helicina antarctica) collected in 1998 and 2007. The 1998 shells were collected by a sediment trap deployed at 2000 m, 47°S, 142°E, and the 2007 shells were collected using nets from mixed-layer waters in the region (44°–54°S, 140°–155°E). Transmission electron microscopy revealed that the shells are composed of a polycrystalline structure, and no obvious porosity was visible. The hardness and modulus of the shells were measured using shell cross-section nanoindentation, across various regions of the shell from the inner to outer whorl. No change in mechanical properties was found with respect to the region of the shell cross-section probed. There was no statistically significant difference in the mean modulus or hardness of the shells between the 1998 and 2007 data sets. No major changes in the mechanical properties of these pteropod shells were detected between the 1998 and 2007 data sets, and we discuss the possible biases in the sampling techniques in complicating our analysis. However, quantifying the mechanical properties and microstructure of calcified may still provide insights into the responses of calcification to environmental changes, such as ocean acidification.     

Ocean acidification and temperature increase impact mussel shell shape and thickness: problematic for protection?

Ocean acidification threatens organisms that produce calcium carbonate shells by potentially generating an under‐saturated carbonate environment. Resultant reduced calcification and growth, and subsequent dissolution of exoskeletons, would raise concerns over the ability of the shell to provide protection for the marine organism under ocean acidification and increased temperatures. We examined the impact of combined ocean acidification and temperature increase on shell formation of the economically important edible mussel Mytilus edulis. Shell growth and thickness along with a shell thickness index and shape analysis were determined. The ability of M. edulis to produce a functional protective shell after 9 months of experimental culture under ocean acidification and increasing temperatures (380, 550, 750, 1000 μatm pCO ₂, and 750, 1000 μatm pCO ₂ + 2°C) was assessed. Mussel shells grown under ocean acidification conditions displayed significant reductions in shell aragonite thickness, shell thickness index, and changes to shell shape (750, 1000 μatm pCO ₂) compared to those shells grown under ambient conditions (380 μatm pCO ₂). Ocean acidification resulted in rounder, flatter mussel shells with thinner aragonite layers likely to be more vulnerable to fracture under changing environments and predation. The changes in shape presented here could present a compensatory mechanism to enhance protection against predators and changing environments under ocean acidification when mussels are unable to grow thicker shells. Here, we present the first assessment of mussel shell shape to determine implications for functional protection under ocean acidification.     

Evolution and biomineralization of pteropod shells

Shelled pteropods, known as sea butterflies, are a group of small gastropods that spend their entire lives swimming and drifting in the open ocean. They build thin shells of aragonite, a metastable polymorph of calcium carbonate. Pteropod shells have been shown to experience dissolution and reduced thickness with a decrease in pH and therefore represent valuable bioindicators to monitor the impacts of ocean acidification. Over the past decades, several studies have highlighted the striking diversity of shell microstructures in pteropods, with exceptional mechanical properties, but their evolution and future in acidified waters remains uncertain. Here, we revisit the body-of-work on pteropod biomineralization, focusing on shell microstructures and their evolution. The evolutionary history of pteropods was recently resolved, and thus it is timely to examine their shell microstructures in such context. We analyse new images of shells from fossils and recent species providing a comprehensive overview of their structural diversity. Pteropod shells are made of the crossed lamellar and prismatic microstructures common in molluscs, but also of curved nanofibers which are proposed to form a helical three-dimensional structure. Our analyses suggest that the curved fibres emerged before the split between coiled and uncoiled pteropods and that they form incomplete to multiple helical turns. The curved fibres are seen as an important trait in the adaptation to a planktonic lifestyle, giving maximum strength and flexibility to the pteropod thin and lightweight shells. Finally, we also elucidate on the candidate biomineralization genes underpinning the shell diversity in these important indicators of ocean health.     

Early Exposure of Bay Scallops (Argopecten irradians) to High CO2 Causes a Decrease in Larval Shell Growth

Ocean acidification, characterized by elevated pCO₂ and the associated decreases in seawater pH and calcium carbonate saturation state (Ω), has a variable impact on the growth and survival of marine invertebrates. Larval stages are thought to be particularly vulnerable to environmental stressors, and negative impacts of ocean acidification have been seen on fertilization as well as on embryonic, larval, and juvenile development and growth of bivalve molluscs. We investigated the effects of high CO₂ exposure (resulting in pH = 7.39, Ω_ar = 0.74) on the larvae of the bay scallop Argopecten irradians from 12 h to 7 d old, including a switch from high CO₂ to ambient CO₂ conditions (pH = 7.93, Ω_ar = 2.26) after 3 d, to assess the possibility of persistent effects of early exposure. The survival of larvae in the high CO₂ treatment was consistently lower than the survival of larvae in ambient conditions, and was already significantly lower at 1 d. Likewise, the shell length of larvae in the high CO₂ treatment was significantly smaller than larvae in the ambient conditions throughout the experiment and by 7 d, was reduced by 11.5%. This study also demonstrates that the size effects of short-term exposure to high CO₂ are still detectable after 7 d of larval development; the shells of larvae exposed to high CO₂ for the first 3 d of development and subsequently exposed to ambient CO₂ were not significantly different in size at 3 and 7 d than the shells of larvae exposed to high CO₂ throughout the experiment.     

Late Quaternary millennial-scale variability in pelagic aragonite preservation off Somalia

In order to better understand Late Quaternary pelagic aragonite preservation in the western Arabian Sea we have investigated a high-resolution sediment core 905 off Somalia. Pteropod preservation is enhanced in times of reduced monsoon-driven productivity, indicated by low amounts of C_org and low barium to aluminium (Ba/Al) ratios. All periods corresponding to Heinrich events in the North Atlantic are represented by maxima in shell preservation of the common pteropod Limacina inflata (LDX values < 2, except for H5-equivalent with a poorer shell preservation, LDX > 2.66). Good shell preservation is also found during stadials at 52.1–53.2, 36, 33.2, and 31.9 ka. Relative abundance of pteropods and their fragments in the coarse fraction reaches maxima during Marine Isotope Stage (MIS) 5.2, during time-equivalents of Heinrich events 4–6 and in stadials at  53,  42.5, and 41.4 ka.On longer time scales, the pteropod abundance corresponds to the ‘Indo-Pacific carbonate preservation type’ with poor preservation during interglacials and better preservation during glacials. Late MIS 5 to early MIS 4 sections (84.1–64.8 ka) and the Late Holocene interval (6.5–0 ka) of core 905 contain only traces of pteropods. The early Holocene (9.2–6.5 ka) part is characterized by low pteropod amounts. Between 64.8 and 43.4 ka strong fluctuations occur and an intermediate average relative pteropod abundance is revealed. Between 43.4 and 9.2 ka the highest amounts in relative pteropod abundance in core 905 are observed. Besides the regional monsoonal influence on deepwater chemistry, changes in deepwater circulation occurring on glacial/interglacial and stadial/interstadial time scales might have affected pteropod preservation. However, it remains elusive whether 1) deep water formation in the Arabian Sea, 2) inflow of Glacial North Atlantic Intermediate Water or 3) change in water mass properties of the Circumpolar Deep Water (which is the water mass currently bathing this site) contributed to the observed pteropod preservation pattern.     

Coral reef calcification: carbonate,bicarbonate and proton flux under conditions of increasing ocean acidification

Data on calcification rate of coral and crustose coralline algae were used to test the proton flux model of calcification. There was a significant correlation between calcification (G) and the ratio of dissolved inorganic carbon (DIC) to proton concentration ([DIC] : [H⁺] ratio). The ratio is tightly correlated with [CO₃²⁻] and with aragonite saturation state (Ω_a). An argument is presented that correlation does not prove cause and effect, and that Ω_a and [CO₃²⁻] have no basic physiological meaning on coral reefs other than a correlation with [DIC] : [H⁺] ratio, which is the driver of G.     

Shellfish Face Uncertain Future in High CO2 World: Influence of Acidification on Oyster Larvae Calcification and Growth in Estuaries

Background

Human activities have increased atmospheric concentrations of carbon dioxide by 36% during the past 200 years. One third of all anthropogenic CO₂ has been absorbed by the oceans, reducing pH by about 0.1 of a unit and significantly altering their carbonate chemistry. There is widespread concern that these changes are altering marine habitats severely, but little or no attention has been given to the biota of estuarine and coastal settings, ecosystems that are less pH buffered because of naturally reduced alkalinity.

Methodology/Principal Findings

To address CO₂-induced changes to estuarine calcification, veliger larvae of two oyster species, the Eastern oyster (Crassostrea virginica), and the Suminoe oyster (Crassostrea ariakensis) were grown in estuarine water under four pCO₂ regimes, 280, 380, 560 and 800 µatm, to simulate atmospheric conditions in the pre-industrial era, present, and projected future concentrations in 50 and 100 years respectively. CO₂ manipulations were made using an automated negative feedback control system that allowed continuous and precise control over the pCO₂ in experimental aquaria. Larval growth was measured using image analysis, and calcification was measured by chemical analysis of calcium in their shells. C. virginica experienced a 16% decrease in shell area and a 42% reduction in calcium content when pre-industrial and end of 21^st century pCO₂ treatments were compared. C. ariakensis showed no change to either growth or calcification. Both species demonstrated net calcification and growth, even when aragonite was undersaturated, a result that runs counter to previous expectations for invertebrate larvae that produce aragonite shells.

Conclusions and Significance

Our results suggest that temperate estuarine and coastal ecosystems are vulnerable to the expected changes in water chemistry due to elevated atmospheric CO₂ and that biological responses to acidification, especially calcifying biota, will be species-specific and therefore much more variable and complex than reported previously.     

Synergistic effects of ocean acidification and warming on overwintering pteropods in the Arctic

Ocean acidification and warming will be most pronounced in the Arctic Ocean. Aragonite shell‐bearing pteropods in the Arctic are expected to be among the first species to suffer from ocean acidification. Carbonate undersaturation in the Arctic will first occur in winter and because this period is also characterized by low food availability, the overwintering stages of polar pteropods may develop into a bottleneck in their life cycle. The impacts of ocean acidification and warming on growth, shell degradation (dissolution), and mortality of two thecosome pteropods, the polar Limacina helicina and the boreal L. retroversa, were studied for the first time during the Arctic winter in the Kongsfjord (Svalbard). The abundance of L. helicina and L. retroversa varied from 23.5 to 120 ind m^?2 and 12 to 38 ind m^?2, and the mean shell size ranged from 920 to 981 μm and 810 to 823 μm, respectively. Seawater was aragonite‐undersaturated at the overwintering depths of pteropods on two out of ten days of our observations. A 7‐day experiment [temperature levels: 2 and 7 °C, pCO₂ levels: 350, 650 (only for L. helicina) and 880 μatm] revealed a significant pCO₂ effect on shell degradation in both species, and synergistic effects between temperature and pCO₂ for L. helicina. A comparison of live and dead specimens kept under the same experimental conditions indicated that both species were capable of actively reducing the impacts of acidification on shell dissolution. A higher vulnerability to increasing pCO₂ and temperature during the winter season is indicated compared with a similar study from fall 2009. Considering the species winter phenology and the seasonal changes in carbonate chemistry in Arctic waters, negative climate change effects on Arctic thecosomes are likely to show up first during winter, possibly well before ocean acidification effects become detectable during the summer season.     

Diverse trends in shell weight of three Southern Ocean pteropod taxa collected with Polar Frontal Zone sediment traps from 1997 to 2007

The impact of ocean acidification on key ocean calcifiers is predicted to be imminent, particularly in high-latitude ecosystems. Long-term field observations are essential to ground truth predictions of change in regional ecosystems. Here, we report on aragonitic pteropods collected to sediment traps at 800 m depth at 54°S, 140°E in the Polar Frontal Zone (PFZ) of the Southern Ocean from 1997 to 2007. Statistically significant trends were not identified in either mass or number flux from 1997 to 2007; however, differences emerged in decadal trends seen in shell weight for each of the three common taxa collected: Limacina helicina antarctica forma antarctica shells became significantly lighter (P < 0.05), L. retroversa australis shells became significantly heavier (P < 0.05) and L. helicina antarctica forma rangi shells did not change significantly. These results suggest that factors other than ocean acidification affect pteropod population variations on decadal timescales, with the potential to either amplify or counter the impact of decreasing aragonite saturation state, at least in the short term. Comparison to sea surface temperature and chlorophyll biomass did not identify these as significant drivers of the observed changes, and attribution across these multiple variables requires better understanding of pteropod physiology and ecology. Our PFZ pelagic pteropod observations provide a reference for evaluation of southern polar pteropod responses to changing ocean conditions in coming decades. Importantly, these data also raise the issue of taxonomic care when monitoring the region for impacts of ocean acidification on calcifiers.     

Calcification is not the Achilles’ heel of cold‐water corals in an acidifying ocean

Ocean acidification is thought to be a major threat to coral reefs: laboratory evidence and CO₂ seep research has shown adverse effects on many coral species, although a few are resilient. There are concerns that cold‐water corals are even more vulnerable as they live in areas where aragonite saturation (Ω_ara) is lower than in the tropics and is falling rapidly due to CO₂ emissions. Here, we provide laboratory evidence that net (gross calcification minus dissolution) and gross calcification rates of three common cold‐water corals, Caryophyllia smithii, Dendrophyllia cornigera, and Desmophyllum dianthus, are not affected by pCO₂ levels expected for 2100 (pCO₂ 1058 μatm, Ω_ara 1.29), and nor are the rates of skeletal dissolution in D. dianthus. We transplanted D. dianthus to 350 m depth (pH_T 8.02; pCO₂ 448 μatm, Ω_ara 2.58) and to a 3 m depth CO₂ seep in oligotrophic waters (pH_T 7.35; pCO₂ 2879 μatm, Ω_ara 0.76) and found that the transplants calcified at the same rates regardless of the pCO₂ confirming their resilience to acidification, but at significantly lower rates than corals that were fed in aquaria. Our combination of field and laboratory evidence suggests that ocean acidification will not disrupt cold‐water coral calcification although falling aragonite levels may affect other organismal physiological and/or reef community processes.     

A nonlinear calcification response to CO2-induced ocean acidification by the coral Oculina arbuscula

Anthropogenic elevation of atmospheric pCO₂ is predicted to cause the pH of surface seawater to decline by 0.3–0.4 units by 2100 AD, causing a 50% reduction in seawater [CO₃ ²⁻] and undersaturation with respect to aragonite in high-latitude surface waters. We investigated the impact of CO₂-induced ocean acidification on the temperate scleractinian coral Oculina arbuscula by rearing colonies for 60 days in experimental seawaters bubbled with air-CO₂ gas mixtures of 409, 606, 903, and 2,856 ppm pCO₂, yielding average aragonite saturation states (Ω_A) of 2.6, 2.3, 1.6, and 0.8. Measurement of calcification (via buoyant weighing) and linear extension (relative to a ¹³⁷Ba/¹³⁸Ba spike) revealed that skeletal accretion was only minimally impaired by reductions in Ω_A from 2.6 to 1.6, although major reductions were observed at 0.8 (undersaturation). Notably, the corals continued accreting new skeletal material even in undersaturated conditions, although at reduced rates. Correlation between rates of linear extension and calcification suggests that reduced calcification under Ω_A = 0.8 resulted from reduced aragonite accretion, rather than from localized dissolution. Accretion of pure aragonite under each Ω_A discounts the possibility that these corals will begin producing calcite, a less soluble form of CaCO₃, as the oceans acidify. The corals’ nonlinear response to reduced Ω_A and their ability to accrete new skeletal material in undersaturated conditions suggest that they strongly control the biomineralization process. However, our data suggest that a threshold seawater [CO₃ ²⁻] exists, below which calcification within this species (and possibly others) becomes impaired. Indeed, the strong negative response of O. arbuscula to Ω_A = 0.8 indicates that their response to future pCO₂-induced ocean acidification could be both abrupt and severe once the critical Ω_A is reached.     

Coral Reefs on the Edge? Carbon Chemistry on Inshore Reefs of the Great Barrier Reef

While increasing atmospheric carbon dioxide (CO₂) concentration alters global water chemistry (Ocean Acidification; OA), the degree of changes vary on local and regional spatial scales. Inshore fringing coral reefs of the Great Barrier Reef (GBR) are subjected to a variety of local pressures, and some sites may already be marginal habitats for corals. The spatial and temporal variation in directly measured parameters: Total Alkalinity (TA) and dissolved inorganic carbon (DIC) concentration, and derived parameters: partial pressure of CO₂ (pCO₂); pH and aragonite saturation state (Ω_ar) were measured at 14 inshore reefs over a two year period in the GBR region. Total Alkalinity varied between 2069 and 2364 µmol kg⁻¹ and DIC concentrations ranged from 1846 to 2099 µmol kg⁻¹. This resulted in pCO₂ concentrations from 340 to 554 µatm, with higher values during the wet seasons and pCO₂ on inshore reefs distinctly above atmospheric values. However, due to temperature effects, Ω_ar was not further reduced in the wet season. Aragonite saturation on inshore reefs was consistently lower and pCO₂ higher than on GBR reefs further offshore. Thermodynamic effects contribute to this, and anthropogenic runoff may also contribute by altering productivity (P), respiration (R) and P/R ratios. Compared to surveys 18 and 30 years ago, pCO₂ on GBR mid- and outer-shelf reefs has risen at the same rate as atmospheric values (∼1.7 µatm yr⁻¹) over 30 years. By contrast, values on inshore reefs have increased at 2.5 to 3 times higher rates. Thus, pCO₂ levels on inshore reefs have disproportionately increased compared to atmospheric levels. Our study suggests that inshore GBR reefs are more vulnerable to OA and have less buffering capacity compared to offshore reefs. This may be caused by anthropogenically induced trophic changes in the water column and benthos of inshore reefs subjected to land runoff.     

Taphonomic windows and molluscan preservation

Recent studies on silicified fossil biotas have suggested that substantial skewing of the molluscan record resulted from early aragonite dissolution in mid-outer carbonate ramp settings. If those rare skeletal lagerstätten are representative, then the quality and completeness of the molluscan record are thrown into doubt. Yet database studies suggest that the bivalve fossil record is actually relatively complete. If so, then biodiversity must be captured by other processes that preserved shells vulnerable to early dissolution, and which operated on a relatively high frequency, i.e., less than the species duration for bivalves.Storm beds, shell plasters and submarine hardgrounds are identified as fossil deposits that can preserve the labile aragonitic component of the fauna and thus represent potential taphonomic windows. Many storm event beds include rich accumulations of shelly benthos. Differences between storm bed faunas and those of the background facies could reflect transportation effects. However, some storm bed assemblages are rich in originally aragonitic infaunal bivalves that are not represented in background facies or more proximal shelf equivalents, and here rapid burial and removal of organic matter by winnowing may be the keys to aragonite shell preservation. Despite Palaeozoic to Cenozoic changes in the thickness and frequency of shell beds that reflect the predominant bioclast producers, shallow infaunas are commonly concentrated together with epifauna in such deposits.Some low energy, organic-rich mud-dominated settings are associated with preservation of aragonitic molluscs. Infaunal bivalves are a prominent component of shell plasters or pavements in such settings, linked to episodic bottom water anoxia. Decaying algal blooms drew the redox boundary up above the sediment–water interface, and brought populations of infaunal bivalves to the surface where they died. Isolated from the oxic taphonomically active zone, the shells were not dissolved and were buried as thin shell layers. In similar settings, aragonitic shells were preserved as moulds through early pyritisation, or even through preservation of original shell aragonite.In oxic environments, bioturbational reworking of surface sediment destroyed moulds of aragonitic shells after early dissolution. In some hardgrounds, these delicate moulds were preserved due to synsedimentary cementation, probably using carbonate released by aragonite dissolution. The examples included here come from both intervals of “calcite” and “aragonite” seas, and it is not possible to assess whether the saturation state (with respect to aragonite) of the ambient sea water played a role in the selective removal of aragonitic shells.While taphonomic windows may have captured the diversity of individual groups, it is clear from quantitative data involving skeletal lagerstätten that the scale of loss from early aragonite dissolution has drastically altered the trophic composition of some fossil assemblages commonly used as the basis for reconstructions of past communities.     

Elevated CO2 affects shell dissolution rate but not calcification rate in a marine snail

As CO₂ levels increase in the atmosphere, so too do they in the sea. Although direct effects of moderately elevated CO₂ in sea water may be of little consequence, indirect effects may be profound. For example, lowered pH and calcium carbonate saturation states may influence both deposition and dissolution rates of mineralized skeletons in many marine organisms. The relative impact of elevated CO₂ on deposition and dissolution rates are not known for many large-bodied organisms. We therefore tested the effects of increased CO₂ levels—those forecast to occur in roughly 100 and 200 years—on both shell deposition rate and shell dissolution rate in a rocky intertidal snail, Nucella lamellosa. Shell weight gain per day in live snails decreased linearly with increasing CO₂ levels. However, this trend was paralleled by shell weight loss per day in empty shells, suggesting that these declines in shell weight gain observed in live snails were due to increased dissolution of existing shell material, rather than reduced production of new shell material. Ocean acidification may therefore have a greater effect on shell dissolution than on shell deposition, at least in temperate marine molluscs.