The rise in atmospheric CO 2 has caused significant decrease in sea surface pH and carbonate ion (CO 22 3 ) concentration. This decrease has a negative effect on calcification in hermatypic corals and other calcifying organisms. We report the results of three laboratory experiments designed specifically to separate the effects of the different carbonate chemistry parameters (pH, CO 22 3 , CO 2 [aq], total alkalinity [A T ], and total inorganic carbon [C T ]) on the calcification, photosynthesis, and respiration of the hermatypic coral Acropora eurystoma. The carbonate system was varied to change pH (7.9-8.5), without changing C T ; C T was changed keeping the pH constant, and C T was changed keeping the pCO 2 constant. In all of these experiments, calcification (both light and dark) was positively correlated with CO 22 3 concentration, suggesting that the corals are not sensitive to pH or C T but to the CO 22 3 concentration. A decrease of ,30% in the CO 22 3 concentration (which is equivalent to a decrease of about 0.2 pH units in seawater) caused a calcification decrease of about 50%. These results suggest that calcification in today's ocean (pCO 2 5 370 ppm) is lower by ,20% compared with preindustrial time (pCO 2 5 280 ppm). An additional decrease of ,35% is expected if atmospheric CO 2 concentration doubles (pCO 2 5 560 ppm). In all of these experiments, photosynthesis and respiration did not show any significant response to changes in the carbonate chemistry of seawater. Based on this observation, we propose a mechanism by which the photosynthesis of symbionts is enhanced by coral calcification at high pH when CO 2 (aq) is low. Overall it seems that photosynthesis and calcification support each other mainly through internal pH regulation, which provides CO 22 3 ions for calcification and CO 2 (aq) for photosynthesis.

Approximately one-quarter of the anthropogenic carbon dioxide released into the atmosphere each year is absorbed by the global oceans, causing measurable declines in surface ocean pH, carbonate ion concentration ([CO3(2-)]), and saturation state of carbonate minerals (Ω). This process, referred to as ocean acidification, represents a major threat to marine ecosystems, in particular marine calcifiers such as oysters, crabs, and corals. Laboratory and field studies have shown that calcification rates of many organisms decrease with declining pH, [CO3(2-)], and Ω. Coral reefs are widely regarded as one of the most vulnerable marine ecosystems to ocean acidification, in part because the very architecture of the ecosystem is reliant on carbonate-secreting organisms. Acidification-induced reductions in calcification are projected to shift coral reefs from a state of net accretion to one of net dissolution this century. While retrospective studies show large-scale declines in coral, and community, calcification over recent decades, determining the contribution of ocean acidification to these changes is difficult, if not impossible, owing to the confounding effects of other environmental factors such as temperature. Here we quantify the net calcification response of a coral reef flat to alkalinity enrichment, and show that, when ocean chemistry is restored closer to pre-industrial conditions, net community calcification increases. In providing results from the first seawater chemistry manipulation experiment of a natural coral reef community, we provide evidence that net community calcification is depressed compared with values expected for pre-industrial conditions, indicating that ocean acidification may already be impairing coral reef growth.

Coral reefs are unique marine ecosystems that form huge morphological structures (frameworks) in today's oceans. These include coral islands (atolls), barrier reefs, and fringing reefs that form the most impressive products of CaCO 3 biomineralization. The framework builders are mainly hermatypic corals, calcareous algae, foraminifera, and mollusks that together are responsible for almost 50% of the net annual CaCO 3 precipitation in the oceans. The reef ecosystem acts as a huge filtration system that extracts plankton from the vast fluxes of ocean water that flow through the framework. The existence of these wave resistant structures in spite of chemical, biological, and physical erosion depends on their exceedingly high rates of calcification. Coral mortality due to bleaching (caused by global warming) and ocean acidification caused by atmospheric CO 2 increase are now the major threats to the existence of these unique ecosystems. When the rates of dissolution and erosion become higher than the rates of precipitation, the entire coral ecosystem starts to collapse and will eventually be reduced to piles of rubble while its magnificent and high diversity fauna will vanish. The loss to nature and to humanity would be unprecedented and it may occur within the next 50 years. In this chapter, we discuss the issue of ocean acidification and its major effects of corals from the cell level to the reef communities. Based on the recently published literature, it can be generalized that calcification in corals is strongly reduced when seawater become slightly acidified. Ocean acidification lowers both the pH and the CO 3 2− ion concentration in the surface ocean, but calcification at the organism level responds mainly to CO 3 2− and not to pH. Most reports show that the symbiotic algae are not sensitive to changes in the carbonate chemistry. The potential mechanisms responsible for coral sensitivity to acidification are either direct input of seawater to the biomineralization site or high sensitivity of the enzymes involved in calcification to pH and/or CO 2 concentrations. Increase in pH at the biomineralization site is most probably the most energy demanding process that is influenced by ocean acidification. While hermatypic corals and other calcifiers reduce their rates of calcification, chemical and biological dissolution increase and hence net calcification of the entire coral reef is decreasing dramatically. Community metabolism in several sites and in field enclosures show in some cases net dissolution. Using the relations between aragonite saturation (W arag ) and community calcification, it is possible to predict that coral reefs globally may start to dissolve when atmospheric CO 2 doubles.

The heavy use of chemicals for agricultural, industrial and domestic purposes has increased the risk of freshwater contamination worldwide. Consequently, the demand for efficient new analytical tools for on-line and on-site water quality monitoring has become particularly urgent. In this study, a small-scale single chamber air-cathode microbial fuel cell (SCMFC), fabricated by rapid prototyping layer-by-layer 3D printing, was tested as a biosensor for continuous water quality monitoring. When acetate was fed as the rate-limiting substrate, the SCMFC acted as a sensor for chemical oxygen demand (COD) in water. The linear detection range was 3-164 ppm, with a sensitivity of 0.05 μA mM-1 cm-2 with respect to the anode total surface area. The response time was as fast as 2.8 minutes. At saturating acetate concentrations (COD>164 ppm), the miniature SCMFC could rapidly detect the presence of cadmium in water with high sensitivity (0.2 μg l-1 cm-2) and a lower detection limit of only 1 μg l-1. The biosensor dynamic range was 1-25 μg l-1. Within this range of concentrations, cadmium affected only temporarily the electroactive biofilm at the anode. When the SCMFCs were again fed with fresh wastewater and no pollutant, the initial steady-state current was recovered within 12 minutes.

community rates of gross photosynthesis (P g ), respiration (R) and net calcification (G net ) were estimated from low-tide slack water measurements of dissolved oxygen, dissolved inorganic carbon and total alkalinity at the historical station DK13 One Tree Island reef, Great Barrier Reef, Australia. Compared to measurements made during the 1960s-1970s at DK13 in the same season, P g increased from 833 to 914 mmol O 2 Ám À2 Ád À1 and P g :R increased from 1.14 to 1.30, indicating that the reef has become more autotrophic. In contrast, G net decreased from 133 mmol CÁm À2 Ád À1 to 74 AE 24 mmol CÁm À2 Ád À1. This decrease stems primarily from the threefold increase in nighttime CaCO 3 dissolution from À2.5 mmolÁmComparison of the benthic community survey results from DK13 and its vicinity conducted during this study and in studies from the 1970s, 1980s and 1990s suggest that there have been no significant changes in the live coral coverage during the past 40 years. The reduced G net most likely reflects the almost threefold increase in dissolution rates, possibly resulting from increased bioerosion due to changes in the biota (e.g., sea cucumbers, boring organisms) and/or from greater chemical dissolution produced by changing abiotic conditions over the past 40 years associated with climate change, such as increased temperatures and ocean acidification. However, at this stage of research on One Tree Island the effects of these changes are not entirely understood.

Ocean acidification poses multiple challenges for coral reefs on molecular to ecological scales, yet previous experimental studies of the impact of projected CO2 concentrations have mostly been done in aquarium systems with corals removed from their natural ecosystem and placed under artificial light and seawater conditions. The Coral–Proto Free Ocean Carbon Enrichment System (CP-FOCE) uses a network of sensors to monitor conditions within each flume and maintain experimental pH as an offset from environmental pH using feedback control on the injection of low pH seawater. Carbonate chemistry conditions maintained in the −0.06 and −0.22 pH offset treatments were significantly different than environmental conditions. The results from this short-term experiment suggest that the CP-FOCE is an important new experimental system to study in situ impacts of ocean acidification on coral reef ecosystems.

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[1] To endure, coral reefs must accumulate CaCO 3 at a rate greater or equal than the sum of mechanically, biologically, and chemically mediated erosion rates. We investigated the potential role of holothurians on the CaCO 3 balance of a coral reef. These deposit feeders process carbonate sand and rubble through their digestive tract and dissolve CaCO 3 as part of their digestive process. In aquarium incubations with Stichopus herrmanni and Holothuria leucospilota total alkalinity increased by 97 AE 13 and 47 AE 7 mmol kg À1 , respectively. This increase was due to CaCO 3 dissolution, 81 AE 13 and 34 AE 6 mmol kg À1 and ammonia secretion, 16 AE 2 and 14 AE 2mmol kg À1, respectively, for these species. Surveys conducted at a long-term monitoring site of community calcification (DK13) on One Tree Reef indicated that the density of sea cucumbers was approximately 1 individual m À2. We used these data and data from surveys at Shark Alley to estimate the dissolution of CaCO 3 by the sea cucumbers at both sites. At DK13 the sea cucumber population was estimated to be responsible for nearly 50% of the nighttime CaCO 3 dissolution, while in Shark Alley for most of the nighttime dissolution. Thus, in a healthy reef, bioeroders dissolution of CaCO 3 sediment appears to be an important component of the natural CaCO 3 turnover and a substantial source of alkalinity as well. This additional alkalinity could partially buffer changes in seawater pH associated with increasing atmospheric CO 2 locally, thus reducing the impact of ocean acidification on coral growth.