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Regnier, P, Friedlingstein P, Ciais P, Mackenzie FT, Gruber N, Janssens IA, Laruelle GG, Lauerwald R, Luyssaert S, Andersson AJ, Arndt S, Arnosti C, Borges AV, Dale AW, Gallego-Sala A, Godderis Y, Goossens N, Hartmann J, Heinze C, Ilyina T, Joos F, LaRowe DE, Leifeld J, Meysman FJR, Munhoven G, Raymond PA, Spahni R, Suntharalingam P, Thullner M.  2013.  Anthropogenic perturbation of the carbon fluxes from land to ocean. Nature Geoscience. 6:597-607.   10.1038/ngeo1830   AbstractWebsite

A substantial amount of the atmospheric carbon taken up on land through photosynthesis and chemical weathering is transported laterally along the aquatic continuum from upland terrestrial ecosystems to the ocean. So far, global carbon budget estimates have implicitly assumed that the transformation and lateral transport of carbon along this aquatic continuum has remained unchanged since pre-industrial times. A synthesis of published work reveals the magnitude of present-day lateral carbon fluxes from land to ocean, and the extent to which human activities have altered these fluxes. We show that anthropogenic perturbation may have increased the flux of carbon to inland waters by as much as 1.0 Pg C yr(-1) since pre-industrial times, mainly owing to enhanced carbon export from soils. Most of this additional carbon input to upstream rivers is either emitted back to the atmosphere as carbon dioxide (similar to 0.4 Pg C yr(-1)) or sequestered in sediments (similar to 0.5 Pg C yr(-1)) along the continuum of freshwater bodies, estuaries and coastal waters, leaving only a perturbation carbon input of similar to 0.1 Pg C yr(-1) to the open ocean. According to our analysis, terrestrial ecosystems store similar to 0.9 Pg C yr(-1) at present, which is in agreement with results from forest inventories but significantly differs from the figure of 1.5 Pg C yr(-1) previously estimated when ignoring changes in lateral carbon fluxes. We suggest that carbon fluxes along the land-ocean aquatic continuum need to be included in global carbon dioxide budgets.

Kuffner, IB, Jokiel PL, Rodgers KS, Andersson AJ, Mackenzie FT.  2012.  An apparent "vital effect" of calcification rate on the Sr/Ca temperature proxy in the reef coral Montipora capitata. Geochemistry Geophysics Geosystems. 13   10.1029/2012gc004128   AbstractWebsite

Measuring the strontium to calcium ratio in coral skeletons reveals information on seawater temperatures during skeletal deposition, but studies have shown additional variables may affect the ratio. Here we measured Sr/Ca in the reef coral Montipora capitata grown in six mesocosms continuously supplied with seawater from the adjacent reef flat. Three mesocosms were ambient controls, and three had seawater chemistry simulating "ocean acidification" (OA). We found that Sr/Ca was not affected by the OA treatment and neither was coral calcification for these small colonies (larger colonies did show an OA effect). The lack of OA effects allowed us to test the hypothesis that coral growth rate can affect Sr/Ca using the natural range in calcification rates of the corals grown at the same temperature. We found that Sr/Ca was inversely related to calcification rate (Sr/Ca = 9.385 - 0.0040 (calcification rate)). Using a previously published calibration curve for this species, a 22 mg d(-1) colony(-1) increase in calcification rate introduced a 1 degrees C warmer temperature estimate, with the 27 corals reporting "temperatures" ranging from 24.9 to 28.9 degrees C, with mean 26.6 +/- 0.9 degrees C standard deviation. Our results lend support to hypotheses invoking kinetic processes and growth rate to explain vital effects on Sr/Ca. However, uncertainty in the slope of the regression of Sr/Ca on calcification and a low R-squared value lead us to conclude that Sr/Ca could still be a useful proxy in this species given sufficient replication or by including growth rate in the calibration.

Sutton, AJ, Feely RA, Maenner-Jones S, Musielwicz S, Osborne J, Dietrich C, Monacci N, Cross J, Bott R, Kozyr A, Andersson AJ, Bates NR, Cai WJ, Cronin MF, DeCarlo EH, Hales B, Howden SD, Lee CM, Manzello DP, McPhaden MJ, Melendez M, Mickett JB, Newton JA, Noakes SE, Noh JH, Olafsdottir SR, Salisbury JE, Send U, Trull TW, Vandemark DC, Weller RA.  2019.  Autonomous seawater pCO(2) and pH time series from 40 surface buoys and the emergence of anthropogenic trends. Earth System Science Data. 11:421-439.   10.5194/essd-11-421-2019   AbstractWebsite

Ship-based time series, some now approaching over 3 decades long, are critical climate records that have dramatically improved our ability to characterize natural and anthropogenic drivers of ocean carbon dioxide (CO2) uptake and biogeochemical processes. Advancements in autonomous marine carbon sensors and technologies over the last 2 decades have led to the expansion of observations at fixed time series sites, thereby improving the capability of characterizing sub-seasonal variability in the ocean. Here, we present a data product of 40 individual autonomous moored surface ocean pCO(2) (partial pressure of CO2) time series established between 2004 and 2013, 17 also include autonomous pH measurements. These time series characterize a wide range of surface ocean carbonate conditions in different oceanic (17 sites), coastal (13 sites), and coral reef (10 sites) regimes. A time of trend emergence (ToE) methodology applied to the time series that exhibit well-constrained daily to interannual variability and an estimate of decadal variability indicates that the length of sustained observations necessary to detect statistically significant anthropogenic trends varies by marine environment. The ToE estimates for seawater pCO(2) and pH range from 8 to 15 years at the open ocean sites, 16 to 41 years at the coastal sites, and 9 to 22 years at the coral reef sites. Only two open ocean pCO(2) time series, Woods Hole Oceanographic Institution Hawaii Ocean Time-series Station (WHOTS) in the subtropical North Pacific and Stratus in the South Pacific gyre, have been deployed longer than the estimated trend detection time and, for these, deseasoned monthly means show estimated anthropogenic trends of 1.9 +/- 0.3 and 1.6 +/- 0.3 mu atm yr(-1), respectively. In the future, it is possible that updates to this product will allow for the estimation of anthropogenic trends at more sites; however, the product currently provides a valuable tool in an accessible format for evaluating climatology and natural variability of surface ocean carbonate chemistry in a variety of regions. Data are available at https.//doi. org/10.7289/V5DB8043 and https.//www.nodc.noaa.gov/ocads/oceans/Moorings/ndp097.html (Sutton et al., 2018).

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Anthony, KRN, Diaz-Pulido G, Verlinden N, Tilbrook B, Andersson AJ.  2013.  Benthic buffers and boosters of ocean acidification on coral reefs. Biogeosciences. 10:4897-4909.   10.5194/bg-10-4897-2013   AbstractWebsite

Ocean acidification is a threat to marine ecosystems globally. In shallow-water systems, however, ocean acidification can be masked by benthic carbon fluxes, depending on community composition, seawater residence time, and the magnitude and balance of net community production (NCP) and calcification (NCC). Here, we examine how six benthic groups from a coral reef environment on Heron Reef (Great Barrier Reef, Australia) contribute to changes in the seawater aragonite saturation state (Omega(a)). Results of flume studies using intact reef habitats (1.2m by 0.4 m), showed a hierarchy of responses across groups, depending on CO2 level, time of day and water flow. At low CO2 (350-450 mu atm), macroalgae (Chnoospora implexa), turfs and sand elevated Omega(a) of the flume water by around 0.10 to 1.20 h(-1) - normalised to contributions from 1m(2) of benthos to a 1m deep water column. The rate of Omega(a) increase in these groups was doubled under acidification (560-700 mu atm) and high flow (35 compared to 8 cm s(-1)). In contrast, branching corals (Acropora aspera) increased Omega(a) by 0.25 h(-1) at ambient CO2 (350-450 mu atm) during the day, but reduced Omega(a) under acidification and high flow. Nighttime changes in Omega(a) by corals were highly negative (0.6-0.8 h(-1)) and exacerbated by acidification. Calcifying macroalgae (Halimeda spp.) raised Omega(a) by day (by around 0.13 h(-1)), but lowered Omega(a) by a similar or higher amount at night. Analyses of carbon flux contributions from benthic communities with four different compositions to the reef water carbon chemistry across Heron Reef flat and lagoon indicated that the net lowering of Omega(a) by coral-dominated areas can to some extent be countered by long water-residence times in neighbouring areas dominated by turfs, macroalgae and carbonate sand.

Eyre, BD, Andersson AJ, Cyronak T.  2014.  Benthic coral reef calcium carbonate dissolution in an acidifying ocean. Nature Climate Change. 4:969-976.   10.1038/nclimate2380   AbstractWebsite

Changes in CaCO3 dissolution due to ocean acidification are potentially more important than changes in calcification to the future accretion and survival of coral reef ecosystems. As most CaCO3 in coral reefs is stored in old permeable sediments, increasing sediment dissolution due to ocean acidification will result in reef loss even if calcification remains unchanged. Previous studies indicate that CaCO3 dissolution could be more sensitive to ocean acidification than calcification by reef organisms. Observed changes in net ecosystem calcification owing to ocean acidification could therefore be due mainly to increased dissolution rather than decreased calcification. In addition, biologically mediated calcification could potentially adapt, at least partially, to future ocean acidification, while dissolution, which is mostly a geochemical response to changes in seawater chemistry, will not adapt. Here, we review the current knowledge of shallow-water CaCO3 dissolution and demonstrate that dissolution in the context of ocean acidification has been largely overlooked compared with calcification.

Lebrato, M, Andersson AJ, Ries JB, Aronson RB, Lamare MD, Koeve W, Oschlies A, Iglesias-Rodriguez MD, Thatje S, Amsler M, Vos SC, Jones DOB, Ruhl HA, Gates AR, McClintock JB.  2016.  Benthic marine calcifiers coexist with CaCO3-undersaturated seawater worldwide. Global Biogeochemical Cycles. 30:1038-1053.   10.1002/2015GB005260   Abstract

Ocean acidification and decreasing seawater saturation state with respect to calcium carbonate (CaCO3) minerals have raised concerns about the consequences to marine organisms that build CaCO3 structures. A large proportion of benthic marine calcifiers incorporate Mg2+ into their skeletons (Mg-calcite), which, in general, reduces mineral stability. The relative vulnerability of some marine calcifiers to ocean acidification appears linked to the relative solubility of their shell or skeletal mineralogy, although some organisms have sophisticated mechanisms for constructing and maintaining their CaCO3 structures causing deviation from this dependence. Nevertheless, few studies consider seawater saturation state with respect to the actual Mg-calcite mineralogy (ΩMg-x) of a species when evaluating the effect of ocean acidification on that species. Here, a global dataset of skeletal mole % MgCO3 of benthic calcifiers and in situ environmental conditions spanning a depth range of 0 m (subtidal/neritic) to 5600 m (abyssal) was assembled to calculate in situ ΩMg-x. This analysis shows that 24% of the studied benthic calcifiers currently experience seawater mineral undersaturation (ΩMg-x < 1). As a result of ongoing anthropogenic ocean acidification over the next 200 to 3000 years, the predicted decrease in seawater mineral saturation will expose approximately 57% of all studied benthic calcifying species to seawater undersaturation. These observations reveal a surprisingly high proportion of benthic marine calcifiers exposed to seawater that is undersaturated with respect to their skeletal mineralogy, underscoring the importance of using species-specific seawater mineral saturation states when investigating the impact of CO2-induced ocean acidification on benthic marine calcification.

Mackenzie, FT, Andersson A.  2010.  Biological control on diagenesis: influence of bacteria and relevance to ocean acidification. Encyclopedia of Geobiology. Abstract
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Mackenzie, FT, Andersson A, et al.  2004.  Boundary exchanges in the global coastal margin: implications for the organic and inorganic carbon cycles. Sea Volume. 13, the global coastal oceanocean: multiscale interdisciplinary processes. ( Robinson A, Brinks K, Eds.)., MA: Harvard University press Abstract
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MeQuaid, JB, Kustka AB, Obornik M, Horak A, McCrow JR, Karas BJ, Zheng H, Kindeberg T, Andersson AJ, Barbeau KA, Allen AE.  2018.  Carbonate-sensitive phytotransferrin controls high-affinity iron uptake in diatoms. Nature. 555:534-+.   10.1038/nature25982   AbstractWebsite

In vast areas of the ocean, the scarcity of iron controls the growth and productivity of phytoplankton(1,2). Although most dissolved iron in the marine environment is complexed with organic molecules(3), picomolar amounts of labile inorganic iron species (labile iron) are maintained within the euphotic zone(4) and serve as an important source of iron for eukaryotic phytoplankton and particularly for diatoms(5). Genome-enabled studies of labile iron utilization by diatoms have previously revealed novel iron responsive transcripts(6,7), including the ferric iron-concentrating protein ISIP2A(8), but the mechanism behind the acquisition of picomolar labile iron remains unknown. Here we show that ISIP2A is a phytotransferrin that independently and convergently evolved carbonate ion-coordinated ferric iron binding. Deletion of ISIP2A disrupts high-affinity iron uptake in the diatom Phaeodactylum tricornutum, and uptake is restored by complementation with human transferrin. ISIP2A is internalized by endocytosis, and manipulation of the seawater carbonic acid system reveals a second order dependence on the concentrations of labile iron and carbonate ions. In P. tricornutum, the synergistic interaction of labile iron and carbonate ions occurs at environmentally relevant concentrations, revealing that carbonate availability co-limits iron uptake. Phytotransferrin sequences have a broad taxonomic distribution(8) and are abundant in marine environmental genomic datasets(9,10), suggesting that acidification-driven declines in the concentration of seawater carbonate ions will have a negative effect on this globally important eukaryotic iron acquisition mechanism.

Marshall, J, Andersson A, Bates N, Dewar W, Doney S, Edson J, Ferrari R, Forget G, Fratantoni D, Gregg M, Joyce T, Kelly K, Lozier S, Lumpkin R, Maze G, Palter J, Samelson R, Silverthorne K, Skyllingstad E, Straneo F, Talley L, Thomas L, Toole J, Weller R, Climode G.  2009.  The CLIMODE FIELD CAMPAIGN Observing the Cycle of Convection and Restratification over the Gulf Stream. Bulletin of the American Meteorological Society. 90:1337-1350.   10.1175/2009bams2706.1   AbstractWebsite
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Andersson, AJ, Bates NR, Jeffries MA, Freeman K, Davidson C, Stringer S, Betzler E, Mackenzie FT.  2013.  Clues from current high CO2 environments on the effects of ocean acidification on CaCO3 preservation. Aquatic Geochemistry.   10.1007/s10498-013-9210-y  
Andersson, AJ, Mackenzie FT, Lerman A.  2005.  Coastal ocean and carbonate systems in the high CO(2) world of the anthropocene. American Journal of Science. 305:875-918.   10.2475/ajs.305.9.875   AbstractWebsite

The behavior of the ocean carbon cycle has been, and will continue to be, modified by the increase in atmospheric CO(2) due to fossil fuel combustion and land-use emissions of this gas. The consequences of a high-CO(2) world and increasing riverine transport of organic matter and nutrients arising from human activities were investigated by means of two biogeochemical box models. Model numerical simulations ranging from the year 1700 to 2300 show that the global coastal ocean changes from a net source to a net sink of atmospheric CO(2) over time; in the 18th and 19th centuries, the direction of the CO(2) flux was from coastal surface waters to the atmosphere, whereas at present or in the near future the net CO(2) flux is into coastal surface waters. These results agree well with recent syntheses of measurements of air-sea CO(2) exchange fluxes from various coastal ocean environments. The model calculations also show that coastal ocean surface water carbonate saturation state would decrease 46 percent by the year 2100 and 73 percent by 2300. Observational evidence from the Pacific and Atlantic Oceans shows that die carbonate saturation state of surface ocean waters has already declined during recent decades. For atolls and other semi-enclosed carbonate systems, the rate of decline depends strongly on the residence time of the water in the system. Based on the experimentally observed positive relationship between saturation state and calcification rate for many calcifying organisms, biogenic production of CaCO(3) may decrease by 42 percent by the year 2100 and by 85 to 90 percent by 2300 relative to its value of about 24 x 10(12) moles C/yr in the year 2000. If the predicted change in carbonate production were to occur along with rising temperatures, it would make it difficult for coral reef and other carbonate systems, to exist as we know them now into future centuries. Because high-latitude, cold-water carbonates presently occur in waters closer to saturation with respect to carbonate minerals than the more strongly supersaturated waters of the lower latitudes, it might be anticipated that the cool-water carbonate systems might feel the effects of rising atmospheric CO(2) (and temperature) before those at lower latitudes. In addition, modeling results show that the carbonate saturation state of coastal sediment pore water will decrease in the future owing to a decreasing pore water pH and increasing CO(2) concentrations attributable to greater deposition and remineralization of land-derived and in situ produced organic matter in sediments. The lowered carbonate saturation state drives selective dissolution of metastable carbonate minerals while a metastable equilibrium is maintained between the pore water and the most soluble carbonate phase present in the sediments. In the future, the average composition of carbonate sediments and cements may change as the more soluble Mg-calcites and aragonite are preferentially dissolved and phases of lower solubility, such as calcites with lower magnesium content, increase in percentage abundance in the sediments.

Andersson, AJ, Mackenzie FT, Lerman A.  2006.  Coastal ocean CO(2)-carbonic acid-carbonate sediment system of the Anthropocene. Global Biogeochemical Cycles. 20   10.1029/2005gb002506   AbstractWebsite

[1] There is little doubt that human activities such as burning of fossil fuels and land use practices have changed and will continue to change the cycling of carbon in the global coastal ocean. In the present study, two biogeochemical box models were used to investigate the consequences of increasing atmospheric CO(2) and subsequent ocean acidification and increasing riverine transport of organic matter and nutrients arising from human activities on land on the global coastal ocean between the years 1700 and 2300. Numerical simulations show that the net flux of CO(2) between coastal ocean surface water and the atmosphere is likely to change during this time from net evasion to net invasion owing to increasing atmospheric CO(2), increasing net ecosystem production arising from increasing nutrient loading to this region, and decreasing net ecosystem calcification due to lower carbonate ion concentration and subsequent lower surface water saturation state with respect to carbonate minerals. Model calculations show that surface water saturation state with respect to calcite will decrease 73% by the year 2300 under a business-as-usual scenario, which in concert with increasing temperature will cause overall biogenic calcification rate to decrease by 90%. Dissolution of carbonate minerals increased by 267% throughout the model simulation. This increase was in part due to increased invasion of atmospheric CO(2), but mainly due to greater deposition and remineralization of land-derived and in situ produced organic matter in the sediments, producing CO(2) that caused pore water pH and carbonate saturation state to decrease. This decrease, in turn, drove selective dissolution of metastable carbonate minerals. As a consequence, the relative carbonate composition of the sediments changed in favor of carbonate phases with lower solubility than that of an average 15 mol% magnesian calcite phase. Model projected changes in surface water carbonate saturation state agree well with observations from the Hawaiian Ocean Time series and the calculated air-sea CO(2) exchanged agrees well with a recent independent estimate of this flux derived from measurements from diverse coastal ecosystems scaled up to the global coastal ocean area.

Lerman, A, Guidry M, Andersson AJ, Mackenzie FT.  2011.  Coastal Ocean Last Glacial Maximum to 2100 CO(2)-Carbonic Acid-Carbonate System: A Modeling Approach. Aquatic Geochemistry. 17:749-773.   10.1007/s10498-011-9146-z   AbstractWebsite

Using coupled terrestrial and coastal zone models, we investigated the impacts of deglaciation and anthropogenic inputs on the CO(2)-H(2)O-CaCO(3) system in global coastal ocean waters from the Last Glacial Maximum (LGM: 18,000 year BP) to the year 2100. With rising sea level and atmospheric CO(2), the carbonate system of coastal ocean water changed significantly. We find that 6 x 10(12) metric tons of carbon were emitted from the coastal ocean, growing due to the sea level rise, from the LGM to late preindustrial time (1700 AD) because of net heterotrophy and calcification processes. This carbon came to reside in the atmosphere and in the growing vegetation on land and in uptake of atmospheric CO(2) through the weathering of rocks on land. It appears that carbonate accumulation, mainly, but not exclusively, in coral reefs from the LGM to late preindustrial time could account for about 24 ppmv of the 100 ppmv rise in atmospheric CO(2), lending some support to the "coral reef hypothesis". In addition, the global coastal ocean is now, or soon will be, a sink of atmospheric CO(2). The temperature rise of 4-5A degrees C since the LGM led to increased weathering rates of inorganic and organic materials on land and enhanced riverine fluxes of total C, N, and P to the coastal ocean of 68%, 108%, and 97%, respectively, from the LGM to late preindustrial time. During the Anthropocene, these trends have been exacerbated owing to rising atmospheric CO(2), due to fossil fuel combustion and land-use practices, other human activities, and rising global temperatures. River fluxes of total reactive C, N, and P are projected to increase from late preindustrial time to the year 2100 by 150%, 380%, and 257%, respectively, modifying significantly the behavior of these element cycles in the coastal ocean, particularly in proximal environments. Despite the fact that the global shoal water carbonate mass has grown extensively since the LGM, the pH(T) (pH values on the total proton scale) of global coastal waters has decreased from similar to 8.35 to similar to 8.18 and the carbonate ion concentration declined by similar to 19% from the LGM to late preindustrial time. The latter represents a rate of decline of about 0.028 mu mol CO(3) (2-) per decade. In comparison, the decrease in coastal water pH(T) from the year 1900 to 2000 was about 8.18-8.08 and is projected to decrease further from about 8.08 to 7.85 between 2000 and 2100, according to the IS92a business-as-usual scenario of CO(2) emissions. Over these 200 years, the carbonate ion concentration will fall by similar to 120 mu mol kg(-1) or 6 mu mol kg(-1) per decade. This decadal rate of decline of the carbonate ion concentration in the Anthropocene is 214 times the average rate of decline for the entire Holocene. Hence, when viewed against the millennial to several millennial timescale of geologic change in the coastal ocean marine carbon system, one can easily appreciate why ocean acidification is the "other CO(2) problem".

Courtney, TA, Andersson AJ, Bates NR, Collins A, Cyronak T, de Putron SJ, Eyre BD, Garley R, Hochberg EJ, Johnson R, Musielewicz S, Noyes TJ, Sabine CL, Sutton AJ, Toncin J, Tribollet A.  2016.  Comparing chemistry and census-based estimates of net ecosystem calcification on a rim reef in Bermuda. Frontiers in Marine Science. 3   10.3389/fmars.2016.00181   Abstract

Coral reef net ecosystem calcification (NEC) has decreased for many Caribbean reefs over recent decades primarily due to a combination of declining coral cover and changing benthic community composition. Chemistry-based approaches to calculate NEC utilize the drawdown of seawater total alkalinity (TA) combined with residence time to calculate an instantaneous measurement of NEC. Census-based approaches combine annual growth rates with benthic cover and reef structural complexity to estimate NEC occurring over annual timescales. Here, NEC was calculated for Hog Reef in Bermuda using both chemistry and census-based NEC techniques to compare the mass-balance generated by the two methods and identify the dominant biocalcifiers at Hog Reef. Our findings indicate close agreement between the annual 2011 census-based NEC 2.35±1.01 kg CaCO3•m-2•y-1 and the chemistry-based NEC 2.23±1.02 kg CaCO3•m-2•y-1 at Hog Reef. An additional record of Hog Reef TA data calculated from an autonomous CO2 mooring measuring pCO2 and modeled pHtotal every 3-hours highlights the dynamic temporal variability in coral reef NEC. This ability for chemistry-based NEC techniques to capture higher frequency variability in coral reef NEC allows the mechanisms driving NEC variability to be explored and tested. Just four coral species, Diploria labyrinthiformis, Pseudodiploria strigosa, Millepora alcicornis, and Orbicella franksi, were identified by the census-based NEC as contributing to 94±19% of the total calcium carbonate production at Hog Reef suggesting these species should be highlighted for conservation to preserve current calcium carbonate production rates at Hog Reef. As coral cover continues to decline globally, the agreement between these NEC estimates suggest that either method, but ideally both methods, may serve as a useful tool for coral reef managers and conservation scientists to monitor the maintenance of coral reef structure and ecosystem services.

Takeshita, Y, Cyronak T, Martz TR, Kindeberg T, Andersson AJ.  2018.  Coral reef carbonate chemistry variability at different functional scales. Frontiers in Marine Science. 5   10.3389/fmars.2018.00175   AbstractWebsite

There is a growing recognition for the need to understand how seawater carbonate chemistry over coral reef environments will change in a high-CO2 world to better assess the impacts of ocean acidification on these valuable ecosystems. Coral reefs modify overlying water column chemistry through biogeochemical processes such as net community organic carbon production (NCR) and calcification (NCC). However, the relative importance and influence of these processes on seawater carbonate chemistry vary across multiple functional scales (defined here as space, time, and benthic community composition), and have not been fully constrained. Here, we use Bermuda as a case study to assess (1) spatiotemporal variability in physical and chemical parameters along a depth gradient at a rim reef location, (2) the spatial variability of total alkalinity (TA) and dissolved inorganic carbon (DIC) over distinct benthic habitats to infer NCC:NCP ratios [< several km(2); rim reef vs. seagrass and calcium carbonate (CaCO3) sediments] on diel timescales, and (3) compare how TA-DIC relationships and NCC:NCP vary as we expand functional scales from local habitats to the entire reef platform (10's of km(2)) on seasonal to interannual timescales. Our results demonstrate that TA-DIC relationships were strongly driven by local benthic metabolism and community composition over diel cycles. However, as the spatial scale expanded to the reef platform, the TA-DIC relationship reflected processes that were integrated over larger spatiotemporal scales, with effects of NCC becoming increasingly more important over NCR. This study demonstrates the importance of considering drivers across multiple functional scales to constrain carbonate chemistry variability over coral reefs.

Eyre, BD, Cyronak T, Drupp P, DeCarlo EH, Sachs JP, Andersson AJ.  2018.  Coral reefs will transition to net dissolving before end of century. Science. 359:908-911.   10.1126/science.aao1118   AbstractWebsite

Ocean acidification refers to the lowering of the ocean's pH due to the uptake of anthropogenic CO2 from the atmosphere. Coral reef calcification is expected to decrease as the oceans become more acidic. Dissolving calciumcarbonate (CaCO3) sands could greatly exacerbate reef loss associated with reduced calcification but is presently poorly constrained. Here we show that CaCO3 dissolution in reef sediments across five globally distributed sites is negatively correlated with the aragonite saturation state (War) of overlying seawater and that CaCO3 sediment dissolution is 10-fold more sensitive to ocean acidification than coral calcification. Consequently, reef sediments globally will transition from net precipitation to net dissolution when seawater War reaches 2.92 +/- 0.16 (expected circa 2050 CE). Notably, some reefs are already experiencing net sediment dissolution.

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Kuffner, IB, Andersson AJ, Jokiel PL, Rodgers KS, Mackenzie FT.  2008.  Decreased abundance of crustose coralline algae due to ocean acidification. Nature Geoscience. 1:114-117.   10.1038/ngeo100   AbstractWebsite

Owing to anthropogenic emissions, atmospheric concentrations of carbon dioxide could almost double between 2006 and 2100 according to business- as- usual carbon dioxide emission scenarios(1). Because the ocean absorbs carbon dioxide from the atmosphere(2-4), increasing atmospheric carbon dioxide concentrations will lead to increasing dissolved inorganic carbon and carbon dioxide in surface ocean waters, and hence acidification and lower carbonate saturation states(2,5). As a consequence, it has been suggested that marine calcifying organisms, for example corals, coralline algae, molluscs and foraminifera, will have difficulties producing their skeletons and shells at current rates(6,7), with potentially severe implications for marine ecosystems, including coral reefs(6,8 - 11). Here we report a seven-week experiment exploring the effects of ocean acidification on crustose coralline algae, a cosmopolitan group of calcifying algae that is ecologically important in most shallow-water habitats(12-14). Six outdoor mesocosms were continuously supplied with sea water from the adjacent reef and manipulated to simulate conditions of either ambient or elevated seawater carbon dioxide concentrations. The recruitment rate and growth of crustose coralline algae were severely inhibited in the elevated carbon dioxide mesocosms. Our findings suggest that ocean acidification due to human activities could cause significant change to benthic community structure in shallow-warm-water carbonate ecosystems.

Zablocki, JA, Andersson AJ, Bates NR.  2011.  Diel Aquatic CO(2) System Dynamics of a Bermudian Mangrove Environment. Aquatic Geochemistry. 17:841-859.   10.1007/s10498-011-9142-3   AbstractWebsite

Mangrove ecosystems play an important, but understudied, role in the cycling of carbon in tropical and subtropical coastal ocean environments. In the present study, we examined the diel dynamics of seawater carbon dioxide (CO(2)) and dissolved oxygen (DO) for a mangrove-dominated marine ecosystem (Mangrove Bay) and an adjacent intracoastal waterway (Ferry Reach) on the island of Bermuda. Spatial and temporal trends in seawater carbonate chemistry and associated variables were assessed from direct measurements of dissolved inorganic carbon, total alkalinity, dissolved oxygen (DO), temperature, and salinity. Diel pCO(2) variability was interpolated across hourly wind speed measurements to determine variability in daily CO(2) fluxes for the month of October 2007 in Bermuda. From these observations, we estimated rates of net sea to air CO(2) exchange for these two coastal ecosystems at 59.8 +/- 17.3 in Mangrove Bay and 5.5 +/- 1.3 mmol m(-2) d(-1) in Ferry Reach. These results highlight the potential for large differences in carbonate system functioning and sea-air CO(2) flux in adjacent coastal environments. In addition, observation of large diel variability in CO(2) system parameters (e.g., mean pCO(2): 390-2,841 mu atm; mean pH(T): 8.05-7.34) underscores the need for careful consideration of diel cycles in long-term sampling regimes and flux estimates.

Page, HN, Andersson AJ, Jokiel PL, Rodgers K’uleiS, Lebrato M, Yeakel K, Davidson C, D’Angelo S, Bahr KD.  2016.  Differential modification of seawater carbonate chemistry by major coral reef benthic communities. Coral Reefs. :1-15.   10.1007/s00338-016-1490-4   AbstractWebsite

Ocean acidification (OA) resulting from uptake of anthropogenic CO2 may negatively affect coral reefs by causing decreased rates of biogenic calcification and increased rates of CaCO3 dissolution and bioerosion. However, in addition to the gradual decrease in seawater pH and Ω a resulting from anthropogenic activities, seawater carbonate chemistry in these coastal ecosystems is also strongly influenced by the benthic metabolism which can either exacerbate or alleviate OA through net community calcification (NCC = calcification – CaCO3 dissolution) and net community organic carbon production (NCP = primary production − respiration). Therefore, to project OA on coral reefs, it is necessary to understand how different benthic communities modify the reef seawater carbonate chemistry. In this study, we used flow-through mesocosms to investigate the modification of seawater carbonate chemistry by benthic metabolism of five distinct reef communities [carbonate sand, crustose coralline algae (CCA), corals, fleshy algae, and a mixed community] under ambient and acidified conditions during summer and winter. The results showed that different communities had distinct influences on carbonate chemistry related to the relative importance of NCC and NCP. Sand, CCA, and corals exerted relatively small influences on seawater pH and Ω a over diel cycles due to closely balanced NCC and NCP rates, whereas fleshy algae and mixed communities strongly elevated daytime pH and Ω a due to high NCP rates. Interestingly, the influence on seawater pH at night was relatively small and quite similar across communities. NCC and NCP rates were not significantly affected by short-term acidification, but larger diel variability in pH was observed due to decreased seawater buffering capacity. Except for corals, increased net dissolution was observed at night for all communities under OA, partially buffering against nighttime acidification. Thus, algal-dominated areas of coral reefs and increased net CaCO3 dissolution may partially counteract reductions in seawater pH associated with anthropogenic OA at the local scale.

Andersson, AJ, Bates NR, Mackenzie FT.  2007.  Dissolution of carbonate sediments under rising pCO(2) and ocean acidification: Observations from Devil's Hole, Bermuda. Aquatic Geochemistry. 13:237-264.   10.1007/s10498-007-9018-8   AbstractWebsite

Rising atmospheric pCO(2) and ocean acidification originating from human activities could result in increased dissolution of metastable carbonate minerals in shallow-water marine sediments. In the present study, in situ dissolution of carbonate sedimentary particles in Devil's Hole, Bermuda, was observed during summer when thermally driven density stratification restricted mixing between the bottom water and the surface mixed layer and microbial decomposition of organic matter in the subthermocline layer produced pCO(2) levels similar to or higher than those levels anticipated by the end of the 21st century. Trends in both seawater chemistry and the composition of sediments in Devil's Hole indicate that Mg-calcite minerals are subject to selective dissolution under conditions of elevated pCO(2). The derived rates of dissolution based on observed changes in excess alkalinity and estimates of vertical eddy diffusion ranged from 0.2 mmol to 0.8 mmol CaCO3 m(-2) h(-1). On a yearly basis, this range corresponds to 175-701 g CaCO3 m(-2) year(-1); the latter rate is close to 50% of the estimate of the current average global coral reef calcification rate of about 1,500 g CaCO3 m(-2) year(-1). Considering a reduction in marine calcification of 40% by the year 2100, or 90% by 2300, as a result of surface ocean acidification, the combination of high rates of carbonate dissolution and reduced rates of calcification implies that coral reefs and other carbonate sediment environments within the 21st and following centuries could be subject to a net loss in carbonate material as a result of increasing pCO(2) arising from burning of fossil fuels.

Pickett, M, Andersson AJ.  2015.  Dissolution rates of biogenic carbonates in natural seawater at different pCO2 conditions: a laboratory study. Aquatic Geochemistry.   10.1007/s10498-015-9261-3   Abstract

The bulk dissolution rates of six biogenic carbonates (goose barnacle, benthic foraminifera, bryozoan, sea urchin, and two types of coralline algae) and a sample of mixed sediment from the Bermuda carbonate platform were measured in natural seawater at pCO2 values ranging from approximately 3000 to 5500 μatm. This range of pCO2 values encompassed values regularly observed in porewaters at a depth of a few cm in carbonate sediments at shallow water depths (<15 m) on the Bermuda carbonate platform. The biogenic carbonates included calcites of varying Mg content (2–17 mol%) and a range of specific surface areas (0.01–2.7 m2 g−1) as determined by BET gas adsorption. Measured rates of dissolution increased with increasing pCO2 treatment for all substrates and ranged from 2.5 to 18 μmol g−1 h−1. The highest rates of dissolution were observed for the bryozoans and the lowest rates for the goose barnacles. The relative ranking in dissolution rates between different substrates was consistent at all pCO2 levels, indicating that substrates dissolve sequentially and that some substrates will be more vulnerable than others to rising CO2 and ocean acidification. Furthermore, dissolution rates were found to increase with increasing Mg content, though the relative dissolution rates were observed to be a function of both Mg content and microstructure (surface area).

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Andersson, AJ, Mackenzie FT, Gattuso J-P.  2011.  Effects of ocean acidification on benthic processes, organisms, and ecosystems. Ocean Acidification. ( Gattuso J, Hansson L, Eds.).:xix,326p.., Oxford England ; New York: Oxford University Press Abstract

The ocean helps moderate climate change thanks to its considerable capacity to store CO2, through the combined actions of ocean physics, chemistry, and biology. This storage capacity limits the amount of human-released CO2 remaining in the atmosphere. As CO2 reacts with seawater, it generates dramatic changes in carbonate chemistry, including decreases in pH and carbonate ions and an increase in bicarbonate ions. The consequences of this overall process, known as "ocean acidification", are raising concerns for the biological, ecological, and biogeochemical health of the world's oceans, as well as for the potential societal implications. This research level text is the first to synthesize the very latest understanding of the consequences of ocean acidification, with the intention of informing both future research agendas and marine management policy. A prestigious list of authors has been assembled, among them the coordinators of major national and international projects on ocean acidification.

Courtney, TA, Lebrato M, Bates NR, Collins A, de Putron SJ, Garley R, Johnson R, Molinero JC, Noyes TJ, Sabine CL, Andersson AJ.  2017.  Environmental controls on modern scleractinian coral and reef-scale calcification. Science Advances. 3   10.1126/sciadv.1701356   AbstractWebsite

Modern reef-building corals sustain a wide range of ecosystem services because of their ability to build calcium carbonate reef systems. The influence of environmental variables on coral calcification rates has been extensively studied, but our understanding of their relative importance is limited by the absence of in situ observations and the ability to decouple the interactions between different properties. We show that temperature is the primary driver of coral colony (Porites astreoides and Diploria labyrinthiformis) and reef-scale calcification rates over a 2-year monitoring period from the Bermuda coral reef. On the basis of multimodel climate simulations (Coupled Model Intercomparison Project Phase 5) and assuming sufficient coral nutrition, our results suggest that P. astreoides and D. labyrinthiformis coral calcification rates in Bermuda could increase throughout the 21st century as a result of gradual warming predicted under a minimum CO2 emissions pathway [ representative concentration pathway (RCP) 2.6] with positive 21st-century calcification rates potentially maintained under a reduced CO2 emissions pathway (RCP 4.5). These results highlight the potential benefits of rapid reductions in global anthropogenic CO2 emissions for 21st-century Bermuda coral reefs and the ecosystem services they provide.

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Bates, NR, Amat A, Andersson AJ.  2010.  Feedbacks and responses of coral calcification on the Bermuda reef system to seasonal changes in biological processes and ocean acidification. Biogeosciences. 7:2509-2530.   10.5194/bg-7-2509-2010   AbstractWebsite

Despite the potential impact of ocean acidification on ecosystems such as coral reefs, surprisingly, there is very limited field data on the relationships between calcification and seawater carbonate chemistry. In this study, contemporaneous in situ datasets of seawater carbonate chemistry and calcification rates from the high-latitude coral reef of Bermuda over annual timescales provide a framework for investigating the present and future potential impact of rising carbon dioxide (CO(2)) levels and ocean acidification on coral reef ecosystems in their natural environment. A strong correlation was found between the in situ rates of calcification for the major framework building coral species Diploria labyrinthiformis and the seasonal variability of [CO(3)(2-)] and aragonite saturation state Omega(aragonite), rather than other environmental factors such as light and temperature. These field observations provide sufficient data to hypothesize that there is a seasonal 'Carbonate Chemistry Coral Reef Ecosystem Feedback' (CREF hypothesis) between the primary components of the reef ecosystem (i.e., scleractinian hard corals and macroalgae) and seawater carbonate chemistry. In early summer, strong net autotrophy from benthic components of the reef system enhance [CO(3)(2-)] and Omega(aragonite) conditions, and rates of coral calcification due to the photosynthetic uptake of CO(2). In late summer, rates of coral calcification are suppressed by release of CO(2) from reef metabolism during a period of strong net heterotrophy. It is likely that this seasonal CREF mechanism is present in other tropical reefs although attenuated compared to high-latitude reefs such as Bermuda. Due to lower annual mean surface seawater [CO(3)(2-)] and Omega(aragonite) in Bermuda compared to tropical regions, we anticipate that Bermuda corals will experience seasonal periods of zero net calcification within the next decade at [CO(3)(2-)] and Omega(aragonite) thresholds of similar to 184 mu moles kg(-1) and 2.65. However, net autotrophy of the reef during winter and spring (as part of the CREF hypothesis) may delay the onset of zero NEC or decalcification going forward by enhancing [CO(3)(2-)] and Omega(aragonite). The Bermuda coral reef is one of the first responders to the negative impacts of ocean acidification, and we estimate that calcification rates for D. labyrinthiformis have declined by > 50% compared to pre-industrial times.