(Table 3) Geochemistry of borehole fluids of ODP Hole 137-504B

Circulation of seawater through basaltic basement for several million years after crustal emplacement has been inferred from studies of surface heat flow, and may play a significant role in the exchange of elements between the oceanic crust and seawater. Without direct observation of the fluid chemistry, interpretations regarding the extent and timing of this exchange must be based on the integrated signal of alteration found in sampled basalts. Much interest has thus been expressed in obtaining and analyzing fluids directly from basaltic formations. It has been proposed that open oceanic boreholes can be used as oceanic groundwater wells to obtain fluids that are circulating within the formation. Water samples were collected from the open borehole in Hole 504B prior to drilling operations on Leg 137, with the original intention of collecting formation fluids from the surrounding basaltic rocks. Past results have yielded ambiguous conclusions as to the origin of the fluids recovered-specifically, whether or not the fluids were true formation fluids or merely the result of reaction of seawater in the borehole environment. The chemistry of eight borehole fluid samples collected during Leg 137 is discussed in this paper. Large changes in major, minor, and isotopic compositions relative to unaltered seawater were observed in the borehole fluids. Compositional changes increased with depth in the borehole. The samples exhibit the effect of simple mixing of seawater, throughout the borehole, with a single reacted fluid component. Analysis and interpretation of the results from Leg 137 in light of past results suggest that the chemical signals observed may originate predominantly from reaction with basaltic rubble residing at the bottom of the hole during the interim between drilling legs. Although this endeavor apparently did not recover formation waters, information on the nature of reaction between seawater and basalt at the prevalent temperatures in Hole 504B (>160°C) has been gained that can be related to reconstruction of the alteration history of the oceanic crust. Isotopic analyses allow calculation of element-specific water/rock mass ratios (Li and Sr) and are related to the extent of chemical exchange between the borehole fluids and basalt.

Seawater carbonate chemistry, photosynthesis and calcification rate during experiments with coral Acropora muricata, 2011

The effect of decreasing aragonite saturation state (Omega Arag) of seawater (elevated pCO2) on calcification rates of Acropora muricata was studied using nubbins prepared from parent colonies located at two sites of La Saline reef (La Réunion Island, western Indian Ocean): a back-reef site (BR) affected by nutrient-enriched groundwater discharge (mainly nitrate), and a reef flat site (RF) with low terrigenous inputs. Protein and chlorophyll a content of the nubbins, as well as zooxanthellae abundance, were lower at RF than BR. Nubbins were incubated at ~27°C over 2 h under sunlight, in filtered seawater manipulated to get differing initial pCO2 (1,440-340 µatm), Omega Arag (1.4-4.0), and dissolved inorganic carbon (DIC) concentrations (2,100-1,850 µmol kg-1). Increasing DIC concentrations at constant total alkalinity (AT) resulted in a decrease in Omega Arag and an increase in pCO2. AT at the beginning of the incubations was kept at a natural level of 2,193 +- 6 µmol kg-1 (mean +- SD). Net photosynthesis (NP) and calcification were calculated from changes in pH and AT during the incubations. Calcification decrease in response to doubling pCO2 relative to preindustrial level was 22% for RF nubbins. When normalized to surface area of the nubbins, (1) NP and calcification were higher at BR than RF, (2) NP increased in high pCO2 treatments at BR compared to low pCO2 treatments, and (3) calcification was not related to Omega Arag at BR. When normalized to NP, calcification was linearly related to Omega Arag at both sites, and the slopes of the relationships were not significantly different. The increase in NP at BR in the high pCO2 treatments may have increased calcification and thus masked the negative effect of low Omega Arag on calcification. Removing the effect of NP variations at BR showed that calcification declined in a similar manner with decreased Omega Arag (increased pCO2) whatever the nutrient loading.

Seawater carbonate chemistry and growth rate during experiments with phylotypes of Symbiodinium (Dinophyceae), 2011

We investigated the effect of elevated partial pressure of CO2 (pCO2) on the photosynthesis and growth of four phylotypes (ITS2 types A1, A13, A2, and B1) from the genus Symbiodinium, a diverse dinoflagellate group that is important, both free-living and in symbiosis, for the viability of cnidarians and is thus a potentially important model dinoflagellate group. The response of Symbiodinium to an elevated pCO2 was phylotype-specific. Phylotypes A1 and B1 were largely unaffected by a doubling in pCO2 in contrast, the growth rate of A13 and the photosynthetic capacity of A2 both increased by ~ 60%. In no case was there an effect of ocean acidification (OA) upon respiration (dark- or light-dependent) for any of the phylotypes examined. Our observations suggest that OA might preferentially select among free-living populations of Symbiodinium, with implications for future symbioses that rely on algal acquisition from the environment (i.e., horizontal transmission). Furthermore, the carbon environment within the host could differentially affect the physiology of different Symbiodinium phylotypes. The range of responses we observed also highlights that the choice of species is an important consideration in OA research and that further investigation across phylogenetic diversity, for both the direction of effect and the underlying mechanism(s) involved, is warranted.

Seawater carbonate chemistry and calcification during tropical reef studies at Younge reef (Great Barrier Reef), 1996

Community metabolism was investigated using a Lagrangian flow respirometry technique on 2 reef flats at Moorea (French Polynesia) during austral winter and Yonge Reef (Great Barrier Reef) during austral summer. The data were used to estimate related air-sea CO2 disequilibrium. A sine function did not satisfactorily model the diel light curves and overestimated the metabolic parameters. The ranges of community gross primary production and respiration (Pg and R; 9 to 15 g C m-2 d-1) were within the range previously reported for reef flats, and community net calcification (G; 19 to 25 g CaCO3 m-2 d-1) was higher than the 'standard' range. The molar ratio of organic to inorganic carbon uptake was 6:1 for both sites. The reef flat at Moorea displayed a higher rate of organic production and a lower rate of calcification compared to previous measurements carried out during austral summer. The approximate uncertainty of the daily metabolic parameters was estimated using a procedure based on a Monte Carlo simulation. The standard errors of Pg,R and Pg/R expressed as a percentage of the mean are lower than 3% but are comparatively larger for E, the excess production (6 to 78%). The daily air-sea CO2 flux (FCO2) was positive throughout the field experiments, indicating that the reef flats at Moorea and Yonge Reef released CO2 to the atmosphere at the time of measurement. FCO2 decreased as a function of increasing daily irradiance.

Seawater carbonate chemistry and biological processed during experiments with corals Porites sp. & Stylophora pistillata, 2010

Uptake of anthropogenic CO2 by the oceans is altering seawater chemistry with potentially serious consequences for coral reef ecosystems due to the reduction of seawater pH and aragonite saturation state (omega arag). The objectives of this long-term study were to investigate the viability of two ecologically important reef-building coral species, massive Porites sp. and Stylophora pistilata, exposed to high pCO2(or low pH) conditions and to observe possible changes in physiologically related parameters as well as skeletal isotopic composition. Fragments of Porites sp. and S. pistilata were kept for 6-14 months under controlled aquarium conditions characterized by normal and elevated pCO2 conditions, corresponding to pHTvalues of 8.09, 7.49, and 7.19, respectively. In contrast with shorter, and therefore more transient experiments, the long experimental timescale achieved in this study ensures complete equilibration and steady state with the experimental environment and guarantees that the data provide insights into viable and stably growing corals. During the experiments, all coral fragments survived and added new skeleton, even at seawater omega arag <1, implying that the coral skeleton is formed by mechanisms under strong biological control. Measurements of boron (B), carbon (C) and oxygen (O) isotopic composition of skeleton, C isotopic composition of coral tissue and symbiont zooxanthellae, along with physiological data (such as skeletal growth, tissue biomass, zooxanthellae cell density and chlorophyll concentration) allow for a direct comparison with corals living under normal conditions and sampled simultaneously. Skeletal growth and zooxanthellae density were found to decrease, whereas coral tissue biomass (measured as protein concentration) and zooxanthellae chlorophyll concentrations increased under high pCO2 (low pH) conditions. Both species showed similar trends of delta11B depletion and delta18O enrichment under reduced pH, whereas the delta13C results imply species-specific metabolic response to high pCO2 conditions. The skeletal delta11B values plot above seawater delta11B vs. pH borate fractionation curves calculated using either the theoretically derived deltaB value of 1.0194 (Kakihana et al., Bull. Chem. Soc. Jpn. 50(1977), 158) or the empirical deltaB value of 1.0272 (Klochko et al., EPSL 248 (2006), 261). However, the effective deltaB must be greater than 1.0200 in order to yield calculated coral skeletal delta11B values for pH conditions where omega arag >1. The delta11B vs. pH offset from the literature seawater delta11B vs. pH fractionation curves suggests a change in the ratio of skeletal material laid down during dark and light calcification and/or an internal pH regulation, presumably controlled by ion-transport enzymes. Finally, seawater pH significantly influences skeletal delta13C and delta18O. This must be taken into consideration when reconstructing paleo-environmental conditions from coral skeleton