Ocean acidification is altering the oceanic carbonate saturation state and threatening the survival of marine calcifying organisms. Production of their calcium carbonate exoskeletons is dependent not only on the environmental seawater carbonate chemistry but also the ability to produce biominerals through proteins. We present shell growth and structural responses by the economically important marine calcifier Mytilus edulis to ocean acidification scenarios (380, 550, 750, 1000 µatm pCO₂). After six months of incubation at 750 µatm pCO₂, reduced carbonic anhydrase protein activity and shell growth occurs in M. edulis. Beyond that, at 1000 µatm pCO₂, biomineralisation continued but with compensated metabolism of proteins and increased calcite growth. Mussel growth occurs at a cost to the structural integrity of the shell due to structural disorientation of calcite crystals. This loss of structural integrity could impact mussel shell strength and reduce protection from predators and changing environments.

Ocean acidification (OA), from seawater uptake of anthropogenic CO_2, has a suite of negative effects on the ability of marine invertebrates to produce and maintain their skeletons. Increased organism pCO₂ causes hypercapnia, an energetically costly physiological stress. OA alters seawater carbonate chemistry, limiting the carbonate available to form the calcium carbonate (CaCO₃) minerals used to build skeletons. The reduced saturation state of CaCO₃ also causes corrosion of CaCO₃ structures. Global change is also accelerating coastal acidification driven by land-run off (e.g. acid soil leachates, tannic acid). Building and maintaining marine biomaterials in the face of changing climate will depend on the balance between calcification and dissolution. Overall, in response to environmental acidification, many calcifiers produce less biomineral and so have smaller body size. Studies of skeleton development in echinoderms and molluscs across life stages show the stunting effect of OA. For corals, linear extension may be maintained, but at the expense of less dense biomineral. Conventional metrics used to quantify growth and calcification need to be augmented by characterisation of the changes to biomineral structure and mechanical integrity caused by environmental acidification. Scanning electron microscopy and microcomputed tomography of corals, tube worms and sea urchins exposed to experimental (laboratory) and natural (vents, coastal run off) acidification show a less dense biomineral with greater porosity and a larger void space. For bivalves, CaCO₃ crystal deposition is more chaotic in response to both ocean and coastal acidification. Biomechanics tests reveal that these changes result in weaker, more fragile skeletons, compromising their vital protective roles. Vulnerabilities differ among taxa and depend on acidification level. Climate warming has the potential to ameliorate some of the negative effects of acidification but may also make matters worse. The integrative morphology-ecomechanics approach is key to understanding how marine biominerals will perform in the face of changing climate.

Ocean acidification (OA) and the resultant changing carbonate saturation states is threatening the formation of calcium carbonate shells and exoskeletons of marine organisms. The production of biominerals in such organisms relies on the availability of carbonate and the ability of the organism to biomineralize in changing environments. To understand how biomineralizers will respond to OA the common blue mussel, Mytilus edulis , was cultured at projected levels of p CO ₂ (380, 550, 750, 1000 µatm) and increased temperatures (ambient, ambient plus 2°C). Nanoindentation (a single mussel shell) and microhardness testing were used to assess the material properties of the shells. Young's modulus ( E ), hardness ( H ) and toughness ( K _IC ) were measured in mussel shells grown in multiple stressor conditions. OA caused mussels to produce shell calcite that is stiffer (higher modulus of elasticity) and harder than shells grown in control conditions. The outer shell (calcite) is more brittle in OA conditions while the inner shell (aragonite) is softer and less stiff in shells grown under OA conditions. Combining increasing ocean p CO ₂ and temperatures as projected for future global ocean appears to reduce the impact of increasing p CO ₂ on the material properties of the mussel shell. OA may cause changes in shell material properties that could prove problematic under predation scenarios for the mussels; however, this may be partially mitigated by increasing temperature.

Biomineral production in marine organisms employs transient phases of amorphous calcium carbonate (ACC) in the construction of crystalline shells. Increasing seawater pCO₂ leads to ocean acidification (OA) with a reduction in oceanic carbonate concentration which could have a negative impact on shell formation and therefore survival. We demonstrate significant changes in the hydrated and dehydrated forms of ACC in the aragonite and calcite layers of Mytilus edulis shells cultured under acidification conditions (1000 μatm pCO₂) compared to present day conditions (380 μatm pCO₂). In OA conditions, Mytilus edulis has more ACC at crystalisation sites. Here, we use the high-spatial resolution of synchrotron X-ray Photo Emission Electron Microscopy (XPEEM) combined with X-ray Absorption Spectroscopy (XAS) to investigate the influence of OA on the ACC formation in the shells of adult Mytilus edulis. Electron Backscatter Diffraction (EBSD) confirms that OA reduces crystallographic control of shell formation. The results demonstrate that OA induces more ACC formation and less crystallographic control in mussels suggesting that ACC is used as a repair mechanism to combat shell damage under OA. However, the resultant reduced crystallographic control in mussels raises concerns for shell protective function under predation and changing environments.