Mechanisms for inorganic carbon acquisition in macroalgal assemblages today could indicate how coastal ecosystems will respond to predicted changes in ocean chemistry due to elevated carbon dioxide (CO 2 ). We identified the proportion of noncalcifying macroalgae with particular carbon use strategies using the natural abundance of carbon isotopes and pH drift experiments in a kelp forest. We also identified all calcifying macroalgae in this system; these were the dominant component of the benthos (by % cover) at all depths and seasons while cover of noncalcareous macroalgae increased at shallower depths and during summer. All large canopy-forming macroalgae had attributes suggestive of active uptake of inorganic carbon and the presence of a CO 2 concentration mechanism (CCM). CCM species covered, on average, 15-45% of the benthos and were most common at shallow depths and during summer. There was a high level of variability in carbon isotope discrimination within CCM species, probably a result of energetic constraints on active carbon uptake in a low light environment. Over 50% of red noncalcifying species exhibited values below À30% suggesting a reliance on diffusive CO 2 uptake and no functional CCM. Non-CCM macroalgae covered on average 0-8.9% of rock surfaces and were most common in deep, low light habitats. Elevated CO 2 has the potential to influence competition between dominant coralline species (that will be negatively affected by increased CO 2 ) and noncalcareous CCM macroalgae (neutral or positive effects) and relatively rare (on a % cover basis) non-CCM species (positive effects). Responses of macroalgae to elevated CO 2 will be strongly modified by light and any responses are likely to be different at times or locations where energy constrains photosynthesis. Increased growth and competitive ability of noncalcareous macroalgae alongside negative impacts of acidification on calcifying species could have major implications for the functioning of coastal reef systems at elevated CO 2 concentrations.

Coastal ecosystems that are characterized by kelp forests encounter daily pH fluctuations, driven by photosynthesis and respiration, which are larger than pH changes owing to ocean acidification (OA) projected for surface ocean waters by 2100. We investigated whether mimicry of biologically mediated diurnal shifts in pH-based for the first time on pH time-series measurements within a kelp forest-would offset or amplify the negative effects of OA on calcifiers. In a 40-day laboratory experiment, the calcifying coralline macroalga, Arthrocardia corymbosa, was exposed to two mean pH treatments (8.05 or 7.65). For each mean, two experimental pH manipulations were applied. In one treatment, pH was held constant. In the second treatment, pH was manipulated around the mean (as a step-function), 0.4 pH units higher during daylight and 0.4 units lower during darkness to approximate diurnal fluctuations in a kelp forest. In all cases, growth rates were lower at a reduced mean pH, and fluctuations in pH acted additively to further reduce growth. Photosynthesis, recruitment and elemental composition did not change with pH, but d 13 C increased at lower mean pH. Including environmental heterogeneity in experimental design will assist with a more accurate assessment of the responses of calcifiers to OA.

Ocean acidification describes changes in the carbonate chemistry of the ocean due to the increased absorption of anthropogenically released CO2 . Experiments to elucidate the biological effects of ocean acidification on algae are not straightforward because when pH is altered, the carbon speciation in seawater is altered, which has implications for photosynthesis and, for calcifying algae, calcification. Furthermore, photosynthesis, respiration, and calcification will themselves alter the pH of the seawater medium. In this review, algal physiologists and seawater carbonate chemists combine their knowledge to provide the fundamental information on carbon physiology and seawater carbonate chemistry required to comprehend the complexities of how ocean acidification might affect algae metabolism. A wide range in responses of algae to ocean acidification has been observed, which may be explained by differences in algal physiology, timescales of the responses measured, study duration, and the method employed to alter pH. Two methods have been widely used in a range of experimental systems: CO2 bubbling and HCl/NaOH additions. These methods affect the speciation of carbonate ions in the culture medium differently; we discuss how this could influence the biological responses of algae and suggest a third method based on HCl/NaHCO3 additions. We then discuss eight key points that should be considered prior to setting up experiments, including which method of manipulating pH to choose, monitoring during experiments, techniques for adding acidified seawater, biological side effects, and other environmental factors. Finally, we consider incubation timescales and prior conditioning of algae in terms of regulation, acclimation, and adaptation to ocean acidification.

Anthropogenically mediated decreases in pH, termed ocean acidification (OA), may be a major threat to marine organisms and communities. Research has focussed mainly on tropical coral reefs, but temperate reefs play a no less important ecological role in colder waters, where OA effects may first be manifest. Herein, we report that trends in pH at the surface of three ecologically important cold-water calcifiers (a primary producer and herbivores), under a range of fluid flows, differ substantially from one another, and for two of the three calcifiers, the pH, during darkness, is lower than the mean projected pH due to OA for the surface waters of the global ocean beyond the year 2100. Using micro-electrodes, we show that each calcifier had a different pH gradient between its surface and mainstream seawater, i.e. within the diffusion boundary layer (DBL) that appears to act as an environmental buffer to mainstream pH. Abalone encountered only mainstream seawater pH, whereas pH at the sea urchins' surface was reduced by~0.35 units. For coralline algae, pH was~0.5 units higher in the light and~0.35 units lower under darkness than in ambient mainstream seawater. This wide range of pH within the DBL of some calcifiers will probably affect their performance under projected future reductions in pH due to OA. Differing exposure to a range of surface pH may result in differential susceptibility of calcifiers to OA. Such fluctuations are no doubt regulated by the interplay of water movement, morphology and metabolic rates (e.g. respiration, calcification and/or photosynthesis). Our study, by considering physics (flow regime), chemistry (pH gradients vs. OA future projections) and biology (trophic level, physiology and morphology), reveals that predicting species-specific responses and subsequent ecosystem restructuring to OA is complex and requires a holistic, eco-mechanical, approach.

Metabolic processes have the potential to modulate the effects of ocean acidification (OA) in nearshore macroalgal beds. We investigated whether natural mixed assemblages of the articulate coralline macroalga Arthrocardia corymbosa and understory crustose coralline algae (CCA) altered pH and O 2 concentrations within and immediately above their canopies. In a unidirectional flume, we tested the effect of water velocity (0-0.1 m s 21 ), bulk seawater pH (ambient pH 8.05, and pH 7.65), and irradiance (photosynthetically saturating light and darkness) on pH and O 2 concentration gradients, and the derived concentration boundary layer (CBL) thickness. At bulk seawater pH 7.65 and slow velocities (0 and 0.015 m s 21 ), pH at the CCA surface increased to 7.90-8.00 in the light. Although these manipulations were short term, this indicates a potential daytime buffering capacity that could alleviate the effects of OA. Photosynthetic activity also increased O 2 concentrations at the surface of the CCA. However, this moderating capacity was flow dependent; the CBL thickness decreased from an average of 26.8 mm from the CCA surface at 0.015 m s 21 to 4.1 mm at 0.04 m s 21 . The reverse trends occurred in the dark, with respiration causing pH and O 2 concentrations to decrease at the CCA surface. At all flow velocities the CBL thicknesses (up to 68 mm) were much greater than those previously published, indicating that the presence of canopies can alter the CBL substantially. In situ, the height of macroalgal canopies can be an order of magnitude larger than those used here, indicating that the degree of buffering to OA will be context dependent.

Ocean acidification (OA) is a reduction in oceanic pH due to increased absorption of anthropogenically produced CO2 . This change alters the seawater concentrations of inorganic carbon species that are utilized by macroalgae for photosynthesis and calcification: CO2 and HCO3 (-) increase; CO3 (2-) decreases. Two common methods of experimentally reducing seawater pH differentially alter other aspects of carbonate chemistry: the addition of CO2 gas mimics changes predicted due to OA, while the addition of HCl results in a comparatively lower [HCO3 (-) ]. We measured the short-term photosynthetic responses of five macroalgal species with various carbon-use strategies in one of three seawater pH treatments: pH 7.5 lowered by bubbling CO2 gas, pH 7.5 lowered by HCl, and ambient pH 7.9. There was no difference in photosynthetic rates between the CO2 , HCl, or pH 7.9 treatments for any of the species examined. However, the ability of macroalgae to raise the pH of the surrounding seawater through carbon uptake was greatest in the pH 7.5 treatments. Modeling of pH change due to carbon assimilation indicated that macroalgal species that could utilize HCO3 (-) increased their use of CO2 in the pH 7.5 treatments compared to pH 7.9 treatments. Species only capable of using CO2 did so exclusively in all treatments. Although CO2 is not likely to be limiting for photosynthesis for the macroalgal species examined, the diffusive uptake of CO2 is less energetically expensive than active HCO3 (-) uptake, and so HCO3 (-) -using macroalgae may benefit in future seawater with elevated CO2 .

Anthropogenically-modulated reductions in pH, termed ocean acidification, could pose a major threat to the physiological performance, stocks, and biodiversity of calcifiers and may devalue their ecosystem services. Recent debate has focussed on the need to develop approaches to arrest the potential negative impacts of ocean acidification on ecosystems dominated by calcareous organisms. In this study, we demonstrate the role of a discrete (i.e. diffusion) boundary layer (DBL), formed at the surface of some calcifying species under slow flows, in buffering them from the corrosive effects of low pH seawater. The coralline macroalga Arthrocardia corymbosa was grown in a multifactorial experiment with two mean pH levels (8.05 ‘ambient’ and 7.65 a worst case ‘ocean acidification’ scenario projected for 2100), each with two levels of seawater flow (fast and slow, i.e. DBL thin or thick). Coralline algae grown under slow flows with thick DBLs (i.e., unstirred with regular replenishment of seawater to their surface) maintained net growth and calcification at pH 7.65 whereas those in higher flows with thin DBLs had net dissolution. Growth under ambient seawater pH (8.05) was not significantly different in thin and thick DBL treatments. No other measured diagnostic (recruit sizes and numbers, photosynthetic metrics, %C, %N, %MgCO3) responded to the effects of reduced seawater pH. Thus, flow conditions that promote the formation of thick DBLs, may enhance the subsistence of calcifiers by creating localised hydrodynamic conditions where metabolic activity ameliorates the negative impacts of ocean acidification.

During austral summer (DJF) 2017/18, the New Zealand region experienced an unprecedented coupled ocean-atmosphere heatwave, covering an area of 4 million km 2 . Regional average air temperature anomalies over land were +2.2°C, and sea surface temperature anomalies reached +3.7°C in the eastern Tasman Sea. This paper discusses the event, including atmospheric and oceanic drivers, the role of anthropogenic warming, and terrestrial and marine impacts. The heatwave was associated with very low wind speeds, reducing upper ocean mixing and allowing heat fluxes from the atmosphere to the ocean to cause substantial warming of the stratified surface layers of the Tasman Sea. The event persisted for the entire austral summer resulting in a 3.8±0.6 km 3 loss of glacier ice in the Southern Alps (the largest annual loss in records back to 1962), very early Sauvignon Blanc wine-grape maturation in Marlborough, and major species disruption in marine ecosystems. The dominant driver was positive Southern Annular Mode (SAM) conditions, with a smaller contribution from La Niña. The long-term trend towards positive SAM conditions, a result of stratospheric ozone depletion and greenhouse gas increase, is thought to have contributed through association with more frequent anticyclonic 'blocking' conditions in the New Zealand region and a more poleward average latitude for the Southern Ocean storm track. The unprecedented heatwave provides a good analogue for possible mean conditions in the late 21st century. The best match suggests this extreme summer may be typical of average New Zealand summer climate for 2081-2100, under the RCP4.5 or RCP6.0 scenario.