Development of laser ablation multi-collector inductively coupled plasma mass spectrometry for boron isotopic measurement in marine biocarbonates: new improvements and application to a modern Porites coral.

RATIONALE: Laser Ablation coupled to Multi-Collector Inductively Coupled Plasma Mass Spectrometry (LA-MC-ICPMS) is a powerful tool for the high-precision measurement of the isotopic ratios of many elements in geological samples, with the isotope ratio ((11) B/(10) B) of boron being used as an indicator of the pH of oceanic waters. Most geological samples or standards are polished and ablation occurs on flat surfaces. However, the shape and the irregularities of marine biocarbonates (e.g., corals, foraminifera) can make precise isotopic measurements of boron difficult. Even after polishing, the porosity properties and the presence of holes or micro-fractures affect the signal and the isotopic ratio when ablating the material, especially in raster mode. METHODS: The effect of porosity and of the crater itself on the (11) B signal and the isotopic ratio acquired by LA-MC-ICPMS in both raster and spot mode was studied. Characterization of the craters was then performed with an optical profilometer to determine their shapes and depths. Surface state effects were examined by analyzing the isotopic fractionation of boron in silicate (NIST-SRM 612 and 610 standards) and in carbonate (corals). RESULTS: Surface irregularities led to a considerable loss of signal when the crater depth exceeded 20 µm. The stability and precision were degraded when ablation occurred in a deep cavity. The effect of laser focusing and of blank correction was also highlighted and our observations indicate that the accuracy of the boron isotopic ratio does not depend on the shape of the surface. After validation of the analytical protocol for boron isotopes, a raster application on a Porites coral, which grew for 18 months in an aquarium after field sampling, was carried out. CONCLUSIONS: This original LA-MC-ICPMS study revealed a well-marked boron isotope ratio temporal variability, probably related to growth rate and density changes, irrespective of the pH of the surrounding seawater. Copyright © 2015 John Wiley & Sons, Ltd.

Effects of elevated temperature and pCO2 on the respiration, biomineralization and photophysiology of the giant clam Tridacna maxima.

Many reef organisms, such as the giant clams, are confronted with global change effects. Abnormally high seawater temperatures can lead to mass bleaching events and subsequent mortality, while ocean acidification may impact biomineralization processes. Despite its strong ecological and socio-economic importance, its responses to these threats still need to be explored. We investigated physiological responses of 4-year-old Tridacna maxima to realistic levels of temperature (+1.5°C) and partial pressure of carbon dioxide (pCO2) (+800 µatm of CO2) predicted for 2100 in French Polynesian lagoons during the warmer season. During a 65-day crossed-factorial experiment, individuals were exposed to two temperatures (29.2°C, 30.7°C) and two pCO2 (430 µatm, 1212 µatm) conditions. The impact of each environmental parameter and their potential synergetic effect were evaluated based on respiration, biomineralization and photophysiology. Kinetics of thermal and/or acidification stress were evaluated by performing measurements at different times of exposure (29, 41, 53, 65 days). At 30.7°C, the holobiont O2 production, symbiont photosynthetic yield and density were negatively impacted. High pCO2 had a significant negative effect on shell growth rate, symbiont photosynthetic yield and density. No significant differences of the shell microstructure were observed between control and experimental conditions in the first 29 days; however, modifications (i.e. less-cohesive lamellae) appeared from 41 days in all temperature and pCO2 conditions. No significant synergetic effect was found. Present thermal conditions (29.2°C) appeared to be sufficiently stressful to induce a host acclimatization response. All these observations indicate that temperature and pCO2 are both forcing variables affecting T. maxima's physiology and jeopardize its survival under environmental conditions predicted for the end of this century.

Seasonal oxygen isotope variations in freshwater bivalve shells as recorders of Amazonian rivers hydrogeochemistry.

Freshwater bivalve shell oxygen isotope values (δ18OS) may act as a recorder of river δ18O variations that can then be interpreted in terms of hydrology (e.g. precipitation-evaporation balance, precipitation and river discharge patterns). We investigated the potential of this proxy measured across the hinge of South American unionid shells: Anodontites elongatus collected in Peru and A. trapesialis in Brazil. The isotopic signatures were reproducible between individuals of the same species. A. trapesialis clearly showed a strong δ18OS cyclicity in accordance with its growth patterns while A. elongatus presented less clear δ18OS with lower amplitude. We confirm that the deposition of successive growth lines and increments is annual, with growth line corresponding to the wet season. Also, we suggest that low amplitude of δ18OS in the A. elongatus shells indicates a habitat close to the river while large amplitude of δ18OS cycles observed in A. trapesialis shells would reflect a floodplain lake habitat, seasonally disconnected from the river and thus subjected to higher seasonal fluctuations in water δ18O. Considering these promising first results, future studies could be directed towards the use of fossil shells to reconstruct the past and present hydrological and geochemical conditions of the Amazon.

Surface ocean pH variations since 1689 CE and recent ocean acidification in the tropical South Pacific.

Increasing atmospheric CO2 from man-made climate change is reducing surface ocean pH. Due to limited instrumental measurements and historical pH records in the world's oceans, seawater pH variability at the decadal and centennial scale remains largely unknown and requires documentation. Here we present evidence of striking secular trends of decreasing pH since the late nineteenth century with pronounced interannual to decadal-interdecadal pH variability in the South Pacific Ocean from 1689 to 2011 CE. High-amplitude oceanic pH changes, likely related to atmospheric CO2 uptake and seawater dissolved inorganic carbon fluctuations, reveal a coupled relationship to sea surface temperature variations and highlight the marked influence of El Niño/Southern Oscillation and Interdecadal Pacific Oscillation. We suggest changing surface winds strength and zonal advection processes as the main drivers responsible for regional pH variability up to 1881 CE, followed by the prominent role of anthropogenic CO2 in accelerating the process of ocean acidification.