Posts Tagged 'methods'

Isotope dilution mass spectrometry for highly precise determination of dissolved inorganic carbon in seawater aiming at climate change studies

Dissolved inorganic carbon (DIC) is one of the most important parameters to be measured in seawaters for climate change studies. Its quantitative assessment requires analytical methodologies with overall uncertainties around 0.05% RSD for clear evaluation of temporal trends. Herein, two alternative isotope dilution mass spectrometry (IDMS) methodologies (online and species-specific) using an isotope ratio mass spectrometer (IRMS) and two calculation procedures for each methodology have been compared. As a result, a new method for the determination of DIC in seawaters, based on species-specific IDMS with isotope pattern deconvolution calculation, was developed and validated. A 13C-enriched bicarbonate tracer was added to the sample and, after equilibration and acidification, the isotope abundances at CO2 masses 44, 45, and 46 were measured on an IRMS instrument. Notably, early spiking allows correcting for evaporations and/or adsorptions during sample preparation and storage and could be carried out immediately after sampling. Full uncertainty budgets were calculated taking into account all the factors involved in the determination (initial weights, concentration and isotope abundances of standards, and final IRMS measurements). The average DIC value obtained for CRM seawater agreed very well with the certified value. Propagated precision obtained ranged from 0.035 to 0.050% RSD for individual sample triplicates. Reproducibility, assessed by three independent experiments carried out in different working days, was excellent as well (−0.01% and 0.057%, error and full combined uncertainty, respectively). Additionally, the approach proposed improves on established methods by simplicity, higher throughput (15 min per sample), and lower volume requirements (10 mL).

Continue reading ‘Isotope dilution mass spectrometry for highly precise determination of dissolved inorganic carbon in seawater aiming at climate change studies’

Assessment of autonomous pH measurements for determining surface seawater partial pressure of CO2

The Southern Ocean Carbon and Climate Observations and Modelling (SOCCOM) program currently operates >80 profiling floats equipped with pH sensors in the Southern Ocean. Theoretically, these floats have the potential to provide unique year‐around estimates of pCO2 derived from pH measurements. Here, we evaluate this approach in the field by comparing pCO2 estimates from pH sensors to directly measured pCO2. We first discuss data from a ship’s underway system which covered a large range in temperature (2‐30°C) and salinity (33.6‐36.5) over 43 days. This pH sensor utilizes the same sensing technology but with different packaging than those on SOCCOM floats. The mean residual varied between ‐4.6 ± 4.1 and 8.6 ± 4.0 (1σ) μatm, depending on how the sensor was calibrated. However, the standard deviation of the residual, interpreted as the ability to track spatiotemporal variability, was consistently < 5 μatm and was independent of the calibration method. Second, we assessed the temporal stability of this approach by comparing pCO2 estimated from four floats over three years to the Hawaii Ocean Time‐series. Good agreement of ‐2.1 ± 10.4 (1σ) µatm was observed, with coherent seasonal cycles. These results demonstrate that pCO2 estimates derived from profiling float pH measurements appear capable of reproducing spatiotemporal variations in surface pCO2 measurements and should provide a powerful observational tool to complement current efforts to understand the seasonal to interannual variability of surface pCO2 in under‐observed regions of the open ocean.

Continue reading ‘Assessment of autonomous pH measurements for determining surface seawater partial pressure of CO2’

The Red Sea simulator: a high‐precision climate change mesocosm with automated monitoring for the long‐term study of coral reef organisms

Experimental systems that enable the controlled perturbation of environmental parameters toward future scenarios are in high demand and becoming increasingly advanced. Herein, we describe the design and assess the performance of a large‐scale, flow‐through, mesocosm system. Located in the northern Gulf of Aqaba, the Red Sea simulator (RSS) was constructed in order to expose local coral reef organisms to future ocean scenarios. Seawater temperature and pH are typically set to a delta from incoming seawater readings and thus follow the diel range. This is achieved through automated monitoring (sensor‐carrying robot) and feedback system and a remote‐controlled user interface. Up to six different temperatures and four pH scenarios can be concomitantly operated in a total of 80 experimental aquaria. In addition, the RSS currently facilitates the manipulation of light intensity, light spectra, nutrient concentration, flow, and feeding regime. Monitoring data show that the system performs well; meeting the user‐defined environmental settings. A variety of reef organisms have been housed in the system for several months. Brooding reef building and soft coral species maintained in the simulator for many months have released planulae in synchrony with field colonies. This system boasts a high degree of replication, potential for multistressor manipulation, typical physiochemical environmental variability, and remotely controlled monitoring and data acquisition. These aspects greatly enhance our ability to make ecologically relevant performance assessments in a changing world.

Continue reading ‘The Red Sea simulator: a high‐precision climate change mesocosm with automated monitoring for the long‐term study of coral reef organisms’

Reviews and syntheses: revisiting the boron systematics of aragonite and their application to coral calcification (update)

The isotopic and elemental systematics of boron in aragonitic coral skeletons have recently been developed as a proxy for the carbonate chemistry of the coral extracellular calcifying fluid. With knowledge of the boron isotopic fractionation in seawater and the B∕Ca partition coefficient (KD) between aragonite and seawater, measurements of coral skeleton δ11B and B∕Ca can potentially constrain the full carbonate system. Two sets of abiogenic aragonite precipitation experiments designed to quantify KD have recently made possible the application of this proxy system. However, while different KD formulations have been proposed, there has not yet been a comprehensive analysis that considers both experimental datasets and explores the implications for interpreting coral skeletons. Here, we evaluate four potential KD formulations: three previously presented in the literature and one newly developed. We assess how well each formulation reconstructs the known fluid carbonate chemistry from the abiogenic experiments, and we evaluate the implications for deriving the carbonate chemistry of coral calcifying fluid. Three of the KD formulations performed similarly when applied to abiogenic aragonites precipitated from seawater and to coral skeletons. Critically, we find that some uncertainty remains in understanding the mechanism of boron elemental partitioning between aragonite and seawater, and addressing this question should be a target of additional abiogenic precipitation experiments. Despite this, boron systematics can already be applied to quantify the coral calcifying fluid carbonate system, although uncertainties associated with the proxy system should be carefully considered for each application. Finally, we present a user-friendly computer code that calculates coral calcifying fluid carbonate chemistry, including propagation of uncertainties, given inputs of boron systematics measured in coral skeleton.

Continue reading ‘Reviews and syntheses: revisiting the boron systematics of aragonite and their application to coral calcification (update)’

Determining coral reef calcification and primary production using automated alkalinity, pH and pCO2 measurements at high temporal resolution

We investigated coral reef carbonate chemistry dynamics and metabolic rates using an automated system that measured total alkalinity (TA, 30 min intervals), pH on the total scale (pHT, 10 min intervals) and the partial pressure of carbon dioxide (pCO2, 1 min intervals) over 2 weeks at Heron Island (Great Barrier Reef, Australia). The calculation of pHT (using the pCO2 and TA pair) and pCO2 (using the pH and TA pair) had similar values to the measured pHT and pCO2 values. In contrast, calculated TA from the pCO2-pH pair showed a large discrepancy with measured TA (average difference between measured and calculated TA = 52 μmol kg−1). High frequency sampling allowed for detailed analysis of the observations and an assessment of optimum sampling intervals required to characterise the net ecosystem calcification (NEC) and production (NEP) using a slack water approach. Depending on the sampling interval (30 min–2 h time steps) used for calculations, the estimated daily NEC and NEP could differ by 12% and 30%, respectively. Abrupt changes in both NEC and NEP were observed at dawn and dusk, with positive NEC during these periods despite negative NEP. Integrating NEC and NEP over a full diel cycle using 1 or 2 h integration time steps resulted in small differences of 2–7% for NEC and 1–3% for NEP. A diel hysteresis pattern rather than a simple linear relationship was observed between the aragonite saturation state (Ωar) and NEC. The observed hysteresis supports recent studies suggesting that short-term observations of seawater Ωar may not be a good predictor of long-term changes in NEC due to ocean acidification. The slope of the DIC to TA relationship was slightly higher (0.33) in 2014 than in an earlier study in 2012 (0.30). The automated, high frequency sampling approach employed here can deliver high precision data and can be used at other coral reef research stations to reveal long-term changes in NEC and NEP potentially driven by ocean acidification, eutrophication or other local changes.

Continue reading ‘Determining coral reef calcification and primary production using automated alkalinity, pH and pCO2 measurements at high temporal resolution’

Coral resistance to ocean acidification linked to increased calcium at the site of calcification

Ocean acidification threatens the persistence of biogenic calcium carbonate (CaCO3) production on coral reefs. However, some coral genera show resistance to declines in seawater pH, potentially achieved by modulating the chemistry of the fluid where calcification occurs. We use two novel geochemical techniques based on boron systematics and Raman spectroscopy, which together provide the first constraints on the sensitivity of coral calcifying fluid calcium concentrations ( ) to changing seawater pH. In response to simulated end-of-century pH conditions, Pocillopora damicornis increased  to as much as 25% above that of seawater and maintained constant calcification rates. Conversely, Acropora youngei displayed less control over in driving calcification has often been neglected, increasing and its calcification rates strongly declined at lower seawater pH. Although the role of  in driving calcification has often been neglected, increasing  may be a key mechanism enabling more resistant corals to cope with ocean acidification and continue to build CaCO3 skeletons in a high-CO2 world.

Continue reading ‘Coral resistance to ocean acidification linked to increased calcium at the site of calcification’

An evaluation of the performance of Sea-Bird scientific’s autonomous SeaFETTM: considerations for the broader oceanographic community

The commercially available Sea-Bird SeaFETTM provides an accessible way for a broad community of researchers to study ocean acidification and obtain robust measurements of seawater pH via the use of an in situ autonomous sensor. There are pitfalls, however, that have been detailed in previous best practices for sensor care, deployment, and data handling. Here, we took advantage of two distinctly different coastal settings to evaluate the Sea-Bird SeaFETTM and examine the multitude of scenarios in which problems may arise confounding the accuracy of measured pH. High-resolution temporal measurements of pH were obtained during 3- to 5-month field deployments in three separate locations (two in south-central, Alaska, USA, and one British Columbia, CA) spanning a broad range of nearshore temperature and salinity conditions. Both the internal and external electrodes onboard the SeaFETTM were evaluated against robust benchtop measurements for accuracy utilizing either the factory calibration, an in situ single-point calibration, or in situ multi-point calibration. In addition, two sensors deployed in parallel in Kasitsna Bay, AK, USA, were compared for inter-sensor variability in order to quantify other factors contributing to SeaFETTM intrinsic inaccuracies. Based on our results, the multi-point calibration method provided the highest accuracy (< 0.025 difference in pH) of pH when compared against benchtop measurements. Spectral analysis of time series data showed that during spring in Alaskan waters, a range of tidal frequencies dominated pH variability, while seasonal oceanographic conditions were the dominant driver in Canadian waters. Further, it is suggested that spectral analysis performed on initial deployments may be able to act as an a posteriori method to better identify appropriate calibration regimes. Based on this evaluation, we provide a comprehensive assessment of the potential sources of uncertainty associated with accuracy and precision of the SeaFETTM electrodes.

Continue reading ‘An evaluation of the performance of Sea-Bird scientific’s autonomous SeaFETTM: considerations for the broader oceanographic community’


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Ocean acidification in the IPCC AR5 WG II

OUP book