Dissolution dominating calcification process in polar pteropods close to the point of aragonite undersaturation

Thecosome pteropods are abundant upper-ocean zooplankton that build aragonite shells. Ocean acidification results in the lowering of aragonite saturation levels in the surface layers, and several incubation studies have shown that rates of calcification in these organisms decrease as a result. This study provides a weight-specific net calcification rate function for thecosome pteropods that includes both rates of dissolution and calcification over a range of plausible future aragonite saturation states (Omega_Ar). We measured gross dissolution in the pteropod Limacina helicina antarctica in the Scotia Sea (Southern Ocean) by incubating living specimens across a range of aragonite saturation states for a maximum of 14 days. Specimens started dissolving almost immediately upon exposure to undersaturated conditions (Omega_Ar,0.8), losing 1.4% of shell mass per day. The observed rate of gross dissolution was different from that predicted by rate law kinetics of aragonite dissolution, in being higher at Var levels slightly above 1 and lower at Omega_Ar levels of between 1 and 0.8. This indicates that shell mass is affected by even transitional levels of saturation, but there is, nevertheless, some partial means of protection for shells when in undersaturated conditions. A function for gross dissolution against Var derived from the present observations was compared to a function for gross calcification derived by a different study, and showed that dissolution became the dominating process even at Omega_Ar levels close to 1, with net shell growth ceasing at an Omega_Ar of 1.03. Gross dissolution increasingly dominated net change in shell mass as saturation levels decreased below 1. As well as influencing their viability, such dissolution of pteropod shells in the surface layers will result in slower sinking velocities and decreased carbon and carbonate fluxes to the deep ocean

Extensive dissolution of live pteropods in the Southern Ocean

The carbonate chemistry of the surface ocean is rapidly changing with ocean acidification, a result of human activities. In the upper layers of the Southern Ocean, aragonite—a metastable form of calcium carbonate with rapid dissolution kinetics—may become undersaturated by 2050 (ref. 2). Aragonite undersaturation is likely to affect aragonite-shelled organisms, which can dominate surface water communities in polar regions. Here we present analyses of specimens of the pteropod Limacina helicina antarctica that were extracted live from the Southern Ocean early in 2008. We sampled from the top 200m of the water column, where aragonite saturation levels were around 1, as upwelled deep water is mixed with surface water containing anthropogenic CO2. Comparing the shell structure with samples from aragonite-supersaturated regions elsewhere under a scanning electron microscope, we found severe levels of shell dissolution in the undersaturated region alone. According to laboratory incubations of intact samples with a range of aragonite saturation levels, eight days of incubation in aragonite saturation levels of 0.94– 1.12 produces equivalent levels of dissolution. As deep-water upwelling and CO2 absorption by surface waters is likely to increase as a result of human activities2,4, we conclude that upper ocean regions where aragonite-shelled organisms are affected by dissolution are likely to expand

Quantifying the Flux of Caco3 and Organic Carbon from the Surface Ocean Using in Situ Measurements of O-2, N-2, Pco(2), and Ph

Ocean acidification from anthropogenic CO2 has focused our attention on the importance of understanding the rates and mechanisms of CaCO3 formation so that changes can be monitored and feedbacks predicted. We present a method for determining the rate of CaCO3 production using in situ measureme nts of fCO(2) and pH in surface waters of the eastern subarctic Pacific Ocean. These quantities were determined on a surface mooring every 3 h for a period of about 9 months in 2007 at Ocean Station Papa (50 degrees N, 145 degrees W). We use the data in a simple surface ocean, mass balance model of dissolved inorganic carbon (DIC) and alkalinity (Alk) to constrain the CaCO3: organic carbon (OC) production ratio to be approximately 0.5. A CaCO3 production rate of 8 mmol CaCO3 m(-2) d(-1) in the summer of 2007 (1.2 mol m(-2) yr(-1)) is derived by combining the CaCO3: OC ratio with the a net organic carbon production rate (2.5 mol C m(-2) yr(-1)) determined from in situ measurements of oxygen and nitrogen gas concentrations measured on the same mooring (Emerson and Stump, 2010). Carbonate chemistry data from a meridional hydrographic section in this area in 2008 indicate that isopycnal surfaces that outcrop in the winter in the subarctic Pacific and deepen southward into the subtropics are a much stronger source for alkalinity than vertical mixing. This pathway has a high enough Alk: DIC ratio to support the CaCO3: OC production rate implied by the fCO(2) and pH data

Linear analysis of the influence of FIR feedback filters on the response of the pulsed digital oscillator

The original publication is available at www.springerlink.comThe objective of this work is to extend the linear analysis of PulsedDigitalOscillators to those topologies having a Finite Impulse Response (FIR) in the feedback loop of the circuit. It will be shown with two specific examples how the overall response of the oscillator can be adjusted to some point by changing the feedback filter, when the resonator presents heavy damping losses. Extensive discrete-time simulations and experimental results obtained with a MEMS cantilever with thermoelectric actuation and piezoresistive position sensing are presented. It will be experimentally shown that the performance of the oscillator is good even below the Nyquist limit

Recent variability of the global ocean carbon sink

We present a new observation-based estimate of the global oceanic carbon dioxide (CO2) sink and its temporal variation on a monthly basis from 1998 through 2011 and at a spatial resolution of 1×1. This sink estimate rests upon a neural network-based mapping of global surface ocean observations of the partial pressure of CO2 (pCO2) from the Surface Ocean CO2 Atlas database. The resulting pCO2 has small biases when evaluated against independent observations in the different ocean basins, but larger randomly distributed differences exist particularly in high latitudes. The seasonal climatology of our neural network-based product agrees overall well with the Takahashi et al. (2009) climatology, although our product produces a stronger seasonal cycle at high latitudes. From our global pCO2 product, we compute a mean net global ocean (excluding the Arctic Ocean and coastal regions) CO2 uptake flux of −1.42 ± 0.53 Pg C yr−1, which is in good agreement with ocean inversion-based estimates. Our data indicate a moderate level of interannual variability in the ocean carbon sink (±0.12 Pg C yr−1, 1𝜎) from 1998 through 2011, mostly originating from the equatorial Pacific Ocean, and associated with the El Nino–Southern Oscillation. Accounting for steady state riverine and Arctic Ocean carbon fluxes our estimate further implies a mean anthropogenic CO2 uptake of −1.99 ± 0.59 Pg C yr−1 over the analysis period. From this estimate plus the most recent estimates for fossil fuel emissions and atmospheric CO2 accumulation, we infer a mean global land sink of −2.82 ± 0.85 Pg C yr−1 over the 1998 through 2011 period with strong interannual variation

Revisiting experimental methods for studies of acidity-dependent ocean sound absorption

Author Posting. © Acoustical Society of America, 2009. This article is posted here by permission of Acoustical Society of America for personal use, not for redistribution. The definitive version was published in Journal of the Acoustical Society of America 125 (2009): 1971-1981, doi:10.1121/1.3089591.The practical usefulness of long-range acoustic measurements of ocean acidity-linked sound absorption is analyzed. There are two applications: Determining spatially-averaged pH via absorption measurement and verifying absorption effects in an area of known pH. The method is a differential-attenuation technique, with the difference taken across frequency. Measurement performance versus mean frequency and range is examined. It is found that frequencies below 500 Hz are optimal. These are lower than the frequency where the measurement would be most sensitive in the absence of noise and signal fluctuation (scintillation). However, attenuation serves to reduce signal-to-noise ratio with increasing distance and frequency, improving performance potential at lower frequencies. Use of low frequency allows longer paths to be used, with potentially better spatial averaging. Averaging intervals required for detection of fluctuations or trends with the required precision are computed

Comparison of CO2 dynamics and air-sea exchange in differing tropical reef environments

Author Posting. © The Author(s), 2013. This is the author's version of the work. It is posted here by permission of Springer for personal use, not for redistribution. The definitive version was published in Aquatic Geochemistry 19 (2013): 371-397, doi:10.1007/s10498-013-9214-7.Note from corresponding author: authors Feely and Shamberger were added after the initial submission, but before the final submission.An array of MAPCO2 buoys, CRIMP-2, Ala Wai, and Kilo Nalu, deployed in the coastal waters of Hawaii have produced multiyear high temporal resolution CO2 records in three different coral reef environments off the island of Oahu, Hawaii. This study, which includes data from June 2008-December 2011, is part of an integrated effort to understand the factors that influence the dynamics of CO2-carbonic acid system parameters in waters surrounding Pacific high island coral reef ecosystems and subject to differing natural and anthropogenic stresses. The MAPCO2 buoys are located on the Kaneohe Bay backreef, and fringing reef sites on the south shore of O’ahu, Hawai’i. The buoys measure CO2 and O2 in seawater and in the atmosphere at 3-hour intervals, as well as other physical and biogeochemical parameters (CTD, chlorophyll-a, turbidity). The buoy records, combined with data from synoptic spatial sampling, have allowed us to examine the interplay between biological cycles of productivity/respiration and calcification/dissolution and biogeochemical and physical forcings on hourly to inter-annual time scales. Air-sea CO2 gas exchange was also calculated to determine if the locations were sources or sinks of CO2 over seasonal, annual, and interannual time periods. Net annualized fluxes for CRIMP-2, Ala Wai, and Kilo Nalu over the entire study period were 1.15 mol C m-2 yr-1, 0.045 mol C m-2 yr-1, and -0.0056 mol C m-2 yr-1, respectively, where positive values indicate a source or a CO2 flux from the water to the atmosphere, and negative values indicate a sink or flux of CO2 from the atmosphere into the water. These values are of similar magnitude to previous estimates in Kaneohe Bay as well as those reported from other tropical reef environments. Total alkalinity (AT) was measured in conjunction with pCO2 and the carbonic acid system was calculated to compare with other reef systems and open ocean values around Hawaii. These findings emphasize the need for high-resolution data of multiple parameters when attempting to characterize the carbonic-acid system in locations of highly variable physical, chemical, and biological parameters (e.g. coastal systems, reefs).This work was supported in part by a grant/cooperative agreement from the National Oceanic and Atmospheric Administration, Project R/IR-3, which is sponsored by the University of Hawaii Sea Grant College Program, SOEST, under Institutional Grant No. NA09OAR4170060 from NOAA Office of Sea Grant, Department of Commerce.2014-11-0

Annual sea-air CO2fluxes in the Bering Sea: insights from new autumn and winter observations of a seasonally ice-covered continental shelf

High-resolution data collected from several programs have greatly increased the spatiotemporal resolution of pCO2(sw) data in the Bering Sea, and provided the first autumn and winter observations. Using data from 2008 to 2012, monthly climatologies of sea-air CO2 fluxes for the Bering Sea shelf area from April to December were calculated, and contributions of physical and biological processes to observed monthly sea-air pCO2 gradients (?pCO2) were investigated. Net efflux of CO2 was observed during November, December, and April, despite the impact of sea surface cooling on ?pCO2. Although the Bering Sea was believed to be a moderate to strong atmospheric CO2 sink, we found that autumn and winter CO2 effluxes balanced 65% of spring and summer CO2 uptake. Ice cover reduced sea-air CO2 fluxes in December, April, and May. Our estimate for ice-cover corrected fluxes suggests the mechanical inhibition of CO2 flux by sea-ice cover has only a small impact on the annual scale (<2%). An important data gap still exists for January to March, the period of peak ice cover and the highest expected retardation of the fluxes. By interpolating between December and April using assumptions of the described autumn and winter conditions, we estimate the Bering Sea shelf area is an annual CO2 sink of ?6.8 Tg C yr?1. With changing climate, we expect warming sea surface temperatures, reduced ice cover, and greater wind speeds with enhanced gas exchange to decrease the size of this CO2 sink by augmenting conditions favorable for greater wintertime outgassing

Biases in the air-sea flux of CO2 resulting from ocean surface temperature gradients

Author Posting. © American Geophysical Union, 2004. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 109 (2004): C08S08, doi:10.1029/2003JC001800.The difference in the fugacities of CO2 across the diffusive sublayer at the ocean surface is the driving force behind the air-sea flux of CO2. Bulk seawater fugacity is normally measured several meters below the surface, while the fugacity at the water surface, assumed to be in equilibrium with the atmosphere, is measured several meters above the surface. Implied in these measurements is that the fugacity values are the same as those across the diffusive boundary layer. However, temperature gradients exist at the interface due to molecular transfer processes, resulting in a cool surface temperature, known as the skin effect. A warm layer from solar radiation can also result in a heterogeneous temperature profile within the upper few meters of the ocean. Here we describe measurements carried out during a 14-day study in the equatorial Pacific Ocean (GasEx-2001) aimed at estimating the gradients of CO2 near the surface and resulting flux anomalies. The fugacity measurements were corrected for temperature effects using data from the ship's thermosalinograph, a high-resolution profiler (SkinDeEP), an infrared radiometer (CIRIMS), and several point measurements at different depths on various platforms. Results from SkinDeEP show that the largest cool skin and warm layer biases occur at low winds, with maximum biases of −4% and +4%, respectively. Time series ship data show an average CO2 flux cool skin retardation of about 2%. Ship and drifter data show significant CO2 flux enhancement due to the warm layer, with maximums occurring in the afternoon. Temperature measurements were compared to predictions based on available cool skin parameterizations to predict the skin-bulk temperature difference, along with a warm layer model.This material is based upon work supported by the NSF under grant OCE-9986724, and by NOAA/OGP grant GC00-226