Carbonic anhydrase, coral calcification and a new model of stable isotope vital effects

The stable isotope compositions of biogenic carbonates have been used for paleoceanographic and paleoclimatic reconstructions for decades, and produced some of the most iconic records in the field. However, we still lack a fully mechanistic understanding of the stable isotope proxies, especially the biological overprint on the environmental signals termed “vital effects”. A ubiquitous feature of stable isotope vital effects in marine calcifying organisms is a strong correlation between δ^(18)O and δ^(13)C in a range of values that are depleted from inorganic calcite/aragonite. Two mechanisms have been proposed to explain this correlation, one based on kinetic isotope effects during CO_2(aq)-HCO_3− inter-conversion, the other based on equilibrium isotope exchange during pH dependent speciation of the dissolved inorganic carbon (DIC) pool. Neither mechanism explains all the stable isotope features observed in biogenic carbonates. Here we present a fully kinetic model of biomineralization and its isotope effects using deep-sea corals as a test organism. A key component of our model is the consideration of the enzyme carbonic anhydrase in catalyzing the CO2(aq)-HCO_3− inter-conversion reactions in the extracellular calcifying fluid (ECF). We find that the amount of carbonic anhydrase not only modulates the carbonate chemistry of the calcifying fluid, but also helps explain the slope of the δ^(18)O-δ^(13)C correlation. Differences in CA activity in the biomineralization process can possibly explain the observed range of δ^(18)O-δ^(13)C slopes in different calcifying organisms. A mechanistic understanding of stable isotope vital effects with numerical models can help us develop better paleoceanographic tracers

Seawater transport during coral biomineralization

Cation transport during skeletal growth is a key process controlling metal/calcium (Me/Ca) paleoproxy behavior in coral. To characterize this transport, cultured corals were transferred into seawater enriched in the rare earth element Tb^(3+) as well as stable isotopes of calcium, strontium, and barium. Subsequent NanoSIMS ion images of each coral skeleton were used to follow uptake dynamics. These images show a continuous region corresponding to new growth that is homogeneously enriched in each tracer. Isotope ratio profiles across the new growth boundary transition rapidly from natural abundance ratios to a ratio matching the enriched culture solution. The location of this transition is the same for each element, within analytical resolution. The synchronous incorporation of all these cations, including the dissimilar ion terbium, which has no known biological function in coral, suggests that: (1) there is cation exchange between seawater and the calcifying fluid, and (2) these elements are influenced by similar transport mechanisms consistent with direct and rapid seawater transport to the site of calcification. Measured using isotope ratio profiles, seawater transport rates differ from place to place on the growing coral skeleton, with calcifying fluid turnover times from 30 min to 5.7 h. Despite these differences, all the elements measured in this study show the same transport dynamics at each location. Using an analytical geochemical model of biomineralization that includes direct seawater transport we constrain the role of active calcium pumping during calcification and we show that the balance between seawater transport and precipitation can explain observed Me/Ca variability in deep-sea coral

Precise overgrowth composition during biomineral culture and inorganic precipitation

We introduce a method to analyze element ratios and isotope ratios in mineral overgrowths. This general technique can quantify environmental controls on proxy behavior for a range of cultured biominerals and can also measure compositional effects during seeded mineral growth. Using a media enriched in multiple stable isotopes, the method requires neither the mass nor the composition of the initial seed or skeleton to be known and involves only bulk isotope measurements. By harnessing the stability and sensitivity of bulk analysis the new approach promises high precision measurements for a range of elements and isotopes. This list includes trace species and select non-traditional stable isotopes, systems where sensitivity and external reproducibility currently limit alternative approaches like secondary ion mass spectrometry (SIMS) and laser ablation mass spectrometry. Since the method separates isotopically labeled growth from unlabeled material, well-choreographed spikes can resolve the compositional effects of different events through time. Among other applications, this feature could be used to separate the impact of day and night on biomineral composition in organisms with photosymbionts

Application of the regression of offspring on mid-parent method to detect associations between single-nucleotide polymorphisms and the beta 2 electroencephalogram phenotype in the COGA data

The beta 2 electroencephalogram (EEG) phenotype is used as a quantitative measure related to alcoholism, and evidence of linkage and association has previously been reported in the Collaborative Study on the Genetics of Alcoholism data. In this study, associations between the beta 2 EEG phenotype and single nucleotide polymorphisms from whole-genome Illumina and Affymetrix panels were investigated with the regression of offspring on mid-parent method to identify significant genetic effects and to estimate their heritability. Separate regressions on father and mother were performed to identify parent-specific effects. Estimates of the heritability of the beta 2 EEG phenotype were 0.68 ± 0.12 and 0.52 ± 0.07 based on father-offspring and mother-offspring pairs, respectively. Significant associations at the 0.0005 level, some of which were parent-specific, were found on chromosomes 1, 2, 5, 6, 7, 8, 11, 12, 15, 16, 17, 18, and 19 with heritability attributable to each SNP ranging from 0.01 to 8%

Sr/Ca and Mg/Ca vital effects correlated with skeletal architecture in a scleractinian deep-sea coral and the role of Rayleigh fractionation

Deep-sea corals are a new tool in paleoceanography with the potential to provide century long records of deep ocean change at sub-decadal resolution. Complicating the reconstruction of past deep-sea temperatures, Mg/Ca and Sr/Ca paleothermometers in corals are also influenced by non-environmental factors, termed vital effects. To determine the magnitude, pattern and mechanism of vital effects we measure detailed collocated Sr/Ca and Mg/Ca ratios, using a combination of micromilling and isotope-dilution ICP-MS across skeletal features in recent samples of Desmophyllum dianthus, a scleractinian coral that grows in the near constant environment of the deep-sea. Sr/Ca variability across skeletal features is less than 5% (2σ relative standard deviation) and variability of Sr/Ca within the optically dense central band, composed of small and irregular aragonite crystals, is significantly less than the surrounding skeleton. The mean Sr/Ca of the central band, 10.6 ± 0.1 mmol/mol (2σ standard error), and that of the surrounding skeleton, 10.58±0.09 mmol/mol, are statistically similar, and agree well with the inorganic aragonite Sr/Ca-temperature relationship at the temperature of coral growth. In the central band, Mg/Ca is greater than 3 mmol/mol, more than twice that of the surrounding skeleton, a general result observed in the relative Mg/Ca ratios of D. dianthus collected from separate oceanographic locations. This large vital effect corresponds to a ∼ 10 °C signal, when calibrated via surface coral Mg/Ca-temperature relationships, and has the potential to complicate paleoreconstructions. Outside the central band, Mg/Ca ratios increase with decreasing Sr/Ca. We explain the correlated behavior of Mg/Ca and Sr/Ca outside the central band by Rayleigh fractionation from a closed pool, an explanation that has been proposed elsewhere, but which is tested in this study by a simple and general relationship. We constrain the initial solution and effective partition coefficients for a Rayleigh process consistent with our accurate Metal/Ca measurements. A process other than Rayleigh fractionation influences Mg in the central band and our data constrain a number of possible mechanisms for the precipitation of this aragonite. Understanding the process affecting tracer behavior during coral biomineralization can help us better interpret paleoproxies in biogenic carbonates and lead to an improved deep-sea paleothermometer

Fluid-Induced Propulsion of Rigid Particles in Wormlike Micellar Solutions

In the absence of inertia, a reciprocal swimmer achieves no net motion in a viscous Newtonian fluid. Here, we investigate the ability of a reciprocally actuated particle to translate through a complex fluid that possesses a network using tracking methods and birefringence imaging. A geometrically polar particle, a rod with a bead on one end, is reciprocally rotated using magnetic fields. The particle is immersed in a wormlike micellar (WLM) solution that is known to be susceptible to the formation of shear bands and other localized structures due to shear-induced remodeling of its microstructure. Results show that the nonlinearities present in this WLM solution break time-reversal symmetry under certain conditions, and enable propulsion of an artificial "swimmer." We find three regimes dependent on the Deborah number (De): net motion towards the bead-end of the particle at low De, net motion towards the rod-end of the particle at intermediate De, and no appreciable propulsion at high De. At low De, where the particle time-scale is longer then the fluid relaxation time, we believe that propulsion is caused by an imbalance in the fluid first normal stress differences between the two ends of the particle (bead and rod). At De~1, however, we observe the emergence of a region of network anisotropy near the rod using birefringence imaging. This anisotropy suggests alignment of the micellar network, which is "locked in" due to the shorter time-scale of the particle relative to the fluid

Deep-sea scleractinian coral age and depth distributions in the northwest Atlantic for the last 225,000 years

Author Posting. © University of Miami - Rosenstiel School of Marine and Atmospheric Science, 2007. This article is posted here by permission of University of Miami - Rosenstiel School of Marine and Atmospheric Science for personal use, not for redistribution. The definitive version was published in Bulletin of Marine Science 81 (2007): 371-391.Deep-sea corals have grown for over 200,000 yrs on the New England Seamounts in the northwest Atlantic, and this paper describes their distribution both with respect to depth and time. Many thousands of fossil scleractinian corals were collected on a series of cruises from 2003-2005; by contrast, live ones were scarce. On these seamounts, the depth distribution of fossil Desmophyllum dianthus (Esper, 1794) is markedly different to that of the colonial scleractinian corals, extending 750 m deeper in the water column to a distinct cut-off at 2500 m. This cut-off is likely to be controlled by the maximum depth of a notch-shaped feature in the seamount morphology. The ages of D. dianthus corals as determined by U-series measurements range from modern to older than 200,000 yrs. The age distribution is not constant over time, and most corals have ages from the last glacial period. Within the glacial period, increases in coral population density at Muir and Manning Sea-mounts coincided with times at which large-scale ocean circulation changes have been documented in the deep North Atlantic. Ocean circulation changes have an effect on coral distributions, but the cause of the link is not known.We gratefully acknowledge the support of The Comer Foundation for Abrupt Climate Change, The Henry Luce Foundation, The American Chemical Society Petroleum Research Fund, NSF Grant Numbers OCE-0096373 and OCE-0095331, and NOAA OE Grant Number A05OAR4601054

A method for eternally dominating strong grids

International audienceIn the eternal domination game, an attacker attacks a vertex at each turn and a team of guards must move a guard to the attacked vertex to defend it. The guards may only move to adjacent vertices and no more than one guard may occupy a vertex. The goal is to determine the eternal domination number of a graph which is the minimum number of guards required to defend the graph against an infinite sequence of attacks. In this paper, we continue the study of the eternal domination game on strong grids. Cartesian grids have been vastly studied with tight bounds for small grids such as 2×n, 3×n, 4×n, and 5×n grids, and recently it was proven in [Lamprou et al., CIAC 2017, 393-404] that the eternal domination number of these grids in general is within O(m + n) of their domination number which lower bounds the eternal domination number. Recently, Finbow et al. proved that the eternal domination number of strong grids is upper bounded by mn 6 + O(m + n). We adapt the techniques of [Lamprou et al., CIAC 2017, 393-404] to prove that the eternal domination number of strong grids is upper bounded by mn 7 + O(m + n). While this does not improve upon a recently announced bound of ⎡m/3⎤ x⎡n/3⎤ + O(m √ n) [Mc Inerney, Nisse, Pérennes, HAL archives, 2018; Mc Inerney, Nisse, Pérennes, CIAC 2019] in the general case, we show that our bound is an improvement in the case where the smaller of the two dimensions is at most 6179