Seawater carbonate chemistry near the Island of Ischia, Italy, 2008

We present the first study of the effects of ocean acidification on settlement of benthic invertebrates and microfauna. Artificial collectors were placed for 1 month along pH gradients at CO2 vents off Ischia (Tyrrhenian Sea, Italy). Seventy-nine taxa were identified from six main taxonomic groups (foraminiferans, nematodes, polychaetes, molluscs, crustaceans and chaetognaths). Calcareous foraminiferans, serpulid polychaetes, gastropods and bivalves showed highly significant reductions in recruitment to the collectors as pCO2 rose from normal (336-341 ppm, pH 8.09-8.15) to high levels (886-5,148 ppm) causing acidified conditions near the vents (pH 7.08-7.79). Only the syllid polychaete Syllis prolifera had higher abundances at the most acidified station, although a wide range of polychaetes and small crustaceans was able to settle and survive under these conditions. A few taxa (Amphiglena mediterranea, Leptochelia dubia, Caprella acanthifera) were particularly abundant at stations acidified by intermediate amounts of CO2 (pH 7.41-7.99). These results show that increased levels of CO2 can profoundly affect the settlement of a wide range of benthic organisms.

Boron isotopes, pH and pCO2 calculation for one Fiji coral specimen Porites (1898-1998), 2012

delta11B results and deduced pH, pCO2 and omega values obtained for a tropical coral specimen Porites collected in 1998 at Yasawa (16°48'S- 177°27'E) on the western side of the Fiji archipelago, location in the north western part of the Pacific Warm Pool. Such Porites specimen grew during the XXth century (1898-1998). Boron isotopes results allowed the reconstruction of surface ocean acidification in the vincinity of Fiji Islands with strong interdecadal influence of the ENSO at regional scale. pHT calculation parameters (Hönisch et al., 2007): a=0 PER MIL; alpha=0.9804; delta11B=39.5 PER MIL; salinity=35.02; pKB from Dickson (1990). pCO2 and omega calculation parameters: TA= 2350 µM; Ca= 10.2 mM; Dickson et al.(2007); Mucci 1983.

Carbonate chemistry, temperature and salinity of Lady Elliot Island Reef 2009-2010

Ocean acidification leads to changes in marine carbonate chemistry that are predicted to cause a decline in future coral reef calcification. Several laboratory and mesocosm experiments have described calcification responses of species and communities to increasing CO2. The few in situ studies on natural coral reefs that have been carried out to date have shown a direct relationship between aragonite saturation state (Omega arag) and net community calcification (Gnet). However, these studies have been performed over a limited range of Omega arag values, where extrapolation outside the observational range is required to predict future changes in coral reef calcification. We measured extreme diurnal variability in carbonate chemistry within a reef flat in the southern Great Barrier Reef, Australia. Omega arag varied between 1.1 and 6.5, thus exceeding the magnitude of change expected this century in open ocean subtropical/tropical waters. The observed variability comes about through biological activity on the reef, where changes to the carbonate chemistry are enhanced at low tide when reef flat waters are isolated from open ocean water. We define a relationship between net community calcification and Omega arag, using our in situ measurements. We find net community calcification to be linearly related to Omega arag, while temperature and nutrients had no significant effect on Gnet. Using our relationship between Gnet and Omega arag, we predict that net community calcification will decline by 55% of its preindustrial value by the end of the century. It is not known at this stage whether exposure to large variability in carbonate chemistry will make reef flat organisms more or less vulnerable to the non-calcifying physiological effects of increasing ocean CO2 and future laboratory studies will need to incorporate this natural variability to address this question.

Image analysis from TEM and AFM micrograph, Table S1, S2, S3, Figure S1, Figure S2

We report on metal enrichment along a natural pH gradient owing to increased CO2 degassing at cold, shal- low seeps of Vulcano Island in the Mediterranean Sea, off Sicily. We assessed composition of unfiltered and filtered seawater (b100 nm) along acidic zones ranging between ambient and pH 5, and showed that most seep derived elements are present as nanoclusters which then aggregate into larger colloids while mixing with ambient seawater along a pH gradient. Size and elemental composition of such naturally occurring nanoparticles assessed by modern characterisation methods were in good agreement with the results from conventional analytical methods. We provide analytical evidence for the presence in the water column of a large fraction of seep derived ele- ments (e.g. approximately 50% of iron, over 80% of Mn, 100% of Cr, S and Zn) in the form of nano sized par- ticles (e.g. b100 nm) even at typical open ocean pHs. We launch in situ sampling protocols and sample preparation procedures for multi-method suitable to obtain accurate measurements on nanoparticles from environmental samples. Based on our results a first insight to the formation of natural nanoparticles at cold CO2 seeps is presented and the persistence of such nano-clusters in the surrounding seawater is stipulated.

Calcareous nannofossil species richness across the Paleocene-Eocene Thermal Maximum

The Paleocene-Eocene Thermal Maximum (PETM, ~5 million years ago) was an interval of global warming and ocean acidification attributed to rapid release and oxidation of buried carbon. We show that the onset of the PETM coincided with a prominent increase in the origination and extinction of calcareous phytoplankton. Yet major perturbation of the surface-water saturation state across the PETM was not detrimental to the survival of most calcareous nannoplankton taxa and did not impart a calcification or ecological bias to the pattern of evolutionary turnover. Instead, the rate of environmental change appears to have driven turnover, preferentially affecting rare taxa living close to their viable limits.

Pleistocene sedimentology of ODP Hole 133-820A from the northeastern Australian margin

A principal objective at Site 820, situated on the outer shelf, upper slope of the northeastern Australian continental margin, was to test the relationships between changes in Pleistocene sea level and sedimentary packages produced on a mixed carbonate-siliciclastic continental margin. To this end, we have examined the downcore distribution of grain size, magnetic susceptibility, and calcium-carbonate content throughout Hole 820A and, in particular, the top 35 meters below the seafloor (mbsf). These data are compared with variations in the oxygen-isotope signal defined for the same hole and are interpreted as indicating sea-level oscillations. The distribution of sand, mud, calcium carbonate of the mud fraction and total sample, and magnetic susceptibility during the last 20,000 yr defines the position of a sea-level regression (41,000-18,000 yr B.P.), a lowstand, early (18,000-9,400 yr B.P.) and late transgressions (9400-900 yr B.P.), and a highstand (4900 yr to the present). The regression is seen first in a high-carbonate content peak. Calcium carbonate constituents mainly comprise skeletal carbonate grains, with abundant planktonic and benthic foraminifers, and lime muds. The lowstand is characterized by a maximum abundance of the sand fraction, which contains dominantly skeletal carbonate grains and a minor abundance of lithoclasts. Sand-sized terrigenous sediments are proposed to have bypassed the continental shelf during a lowstand of sea level. Sedimentation rates throughout the regression and lowstand are low (3.0 cm/k.y.). The early transgression, marked by highest values in magnetic susceptibility, displays a rapid increase in sedimentation rate that coincided with an increase in terrigenous mud. Highest sedimentation rates of 82.3 cm/k.y. occurred during the late transgression, with increasing percentages of lime-mud. A decrease in noncarbonate constituents in the mud fraction during the late transgression and highstand of sea level is thought to be the result of restricted inner-shelf sedimentation of terrigenous sediments. The same relationship is also seen in the major sea-level oscillation, which is interpreted as isotope stage 6.

Sedimentological and benthic foraminiferal data pertaining to ODP Holes 208-1262A and 208-1263C

Eocene Thermal Maximum 2 (ETM2) occurred ~1.8 Myr after the Paleocene Eocene Thermal Maximum (PETM) and, like the PETM, was characterized by a negative carbon isotope excursion coupled with warming. We combined benthic foraminiferal and sedimentological records for Southeast Atlantic Sites 1263 (1500 m paleodepth) and 1262 (3600 m paleodepth) to show that benthic foraminiferal diversity and accumulation rates declined more precipitously and severely at the shallower site during peak ETM2. The sites are in close proximity, so differences in surface productivity cannot have caused this differential effect. Instead, on the basis of an analysis of climate modelling experiments, we infer that changes in ocean circulation pattern across ETM2 may have resulted in more pronounced warming at intermediate depths (Site 1263). The effects of more pronounced warming include increased metabolic rates, leading to a decrease in effective food supply and increased deoxygenation, thus potentially explaining the more severe benthic impacts at Site 1263. In response to more severe benthic disturbance, bioturbation may have decreased at Site 1263 as compared to Site 1262, hence differentially affecting the bulk carbonate record. We use a sediment-enabled Earth system model to test whether a reduction in bioturbation and/or the likely reduced carbonate saturation of more poorly ventilated waters can explain the more extreme excursion in bulk d13C and sharper transition in wt% CaCO3 at Site 1263. We find that both enhanced acidification and reduced bioturbation during peak ELMO conditions are needed to account for the observed features. Our combined ecological and modelling analysis illustrates the potential role of ocean circulation changes in amplifying local environmental changes and driving temporary, but drastic, loss of benthic biodiversity and abundance.

Reefs shift from net accretion to net erosion along a natural environmental gradient

Coral reefs persist in an accretion-erosion balance and ocean acidification resulting from anthropogenic CO2 emissions threatens to shift this balance in favor of net reef erosion. Corals and calcifying algae, largely responsible for reef accretion, are vulnerable to environmental changes associated with ocean acidification, but the direct effects of lower pH on reef erosion has received less attention, particularly in the context of known drivers of bioerosion and natural variability. This study examines the balance between reef accretion and erosion along a well-characterized natural environmental gradient in Kane'ohe Bay, Hawai'i using experimental blocks of coral skeleton. Comparing before and after micro-computed tomography (µCT) scans to quantify net accretion and erosion, we show that, at the small spatial scale of this study (tens of meters), pH was a better predictor of the accretion-erosion balance than environmental drivers suggested by prior studies, including resource availability, temperature, distance from shore, or depth. In addition, this study highlights the fine-scale variation of pH in coastal systems and the importance of microhabitat variation for reef accretion and erosion processes. We demonstrate significant changes in both the mean and variance of pH on the order of meters, providing a local perspective on global increases in pCO2. Our findings suggest that increases in reef erosion, combined with expected decreases in calcification, will accelerate the shift of coral reefs to an erosion-dominated system in a high-CO2 world. This shift will make reefs increasingly susceptible to storm damage and sea-level rise, threatening the maintenance of the ecosystem services that coral reefs provide.