Stable isotopes in deep-sea corals and a new mechanism for “vital effects”

Offsets from isotopic equilibrium in biogenic carbonates have complicated paleoclimate reconstructions for decades. A new archive of climate, deep-sea corals, is used to evaluate the calcification processes, independent of photosynthesis, that contribute to these offsets. Carbon and oxygen stable isotope data from six modern deep-sea corals show strong linear trends between δ¹³C and δ¹⁸O. Slopes of these trends between samples are similar and range between 1.9 to 2.6 for Δδ¹³C/Δδ¹⁸O. Linear trends intersect isotopic equilibrium for δ¹⁸O and are slightly depleted for δ¹³C. Variations in the isotopic ratios are strongly correlated with the density banding structure. Isotopically depleted aragonite is associated with light, quickly precipitating bands, whereas isotopically enriched points correspond to slowly accumulating, less dense aragonite. The densest white band at the trabecular center is furthest from isotopic equilibrium for both carbon and oxygen. Data from this region fall off the linear trend between δ¹⁸O and δ¹³C. This deviation, where δ¹³C remains constant while the δ¹⁸O continues to decrease, does not support “vital effect” mechanisms that call upon kinetic fractionation to explain offsets from isotopic equilibrium. We propose a new mechanism for vital effects in these deep-sea corals that is based on a thermodynamic response to a biologically induced pH gradient in the calcifying region.     

The Ultimate CCD for Laser Guide Star Wavefront Sensing on Extremely Large Telescopes

All of the extremely large telescopes (ELTs) will utilize sodium laser guide star (LGS) adaptive optics (AO) systems. Most of these telescopes plan to use the Shack-Hartmann approach for wavefront sensing. In these AO systems, the laser spots in subapertures at the edge of the pupil will suffer from spot elongation due to the 10 km extent of the sodium layer and the large separation from the projection laser. This spot elongation will severely degrade the performance of standard geometry wavefront sensing systems. In this paper, we present a CCD with custom pixel morphology that aligns the pixels of each subaperture with the radial extension of the LGS spot. This CCD design will give better performance than a standard geometry CCDs for continuous wave lasers. In addition, this CCD design is optimal for a pulsed sodium laser. The pixel geometry enables each subaperture to follow a laser pulse traversing the sodium layer, providing optimal sampling of a limited number of detected photons. In addition to novel pixel layout, this CCD will also incorporate experimental JFET sense amplifiers and use CMOS design approaches to simplify the routing of biases, clocks and video output. This CCD will attain photon-noise limited performance at high frame rates, and is being incorporated in the plans for the Thirty Meter Telescope (TMT).     

The production of ions by splashing in an electric field

Summary Measurements of the concentration of small ions near the ground showed that large numbers of «ions» of sign opposite to that of the potential gradient were produced in rain. A series of laboratory experiments designed to examine the processes involved, showed that the ions were produced by the disintegration of films of water when drops splash, and a determination was made of the dependence of the charge released by individual drops on the parameters involved.The paper will be published elsewhere.     

C-O bonds in carbonate minerals: A new kind of paleothermometer

The abundance of the doubly substituted CO₂ isotopologue, ¹³C¹⁸O¹⁶O, in CO₂ produced by phosphoric acid digestion of synthetic, inorganic calcite and natural, biogenic aragonite is proportional to the concentration of ¹³C-¹⁸O bonds in reactant carbonate, and the concentration of these bonds is a function of the temperature of carbonate growth. This proportionality can be described between 1 and 50 °C by the function: Δ₄₇ = 0.0592 · 10⁶ · T⁻² − 0.02, where Δ₄₇ is the enrichment, in per mil, of ¹³C¹⁸O¹⁶O in CO₂ relative to the amount expected for a stochastic (random) distribution of isotopes among all CO₂ isotopologues, and T is the temperature in Kelvin. This relationship can be used for a new kind of carbonate paleothermometry, where the temperature-dependent property of interest is the state of ordering of ¹³C and ¹⁸O in the carbonate lattice (i.e., bound together vs. separated into different CO₃²⁻ units), and not the bulk δ¹⁸O or δ¹³C values. Current analytical methods limit precision of this thermometer to ca. ± 2 °C, 1σ. A key feature of this thermometer is that it is thermodynamically based, like the traditional carbonate-water paleothermometer, and so is suitable for interpolation and even modest extrapolation, yet is rigorously independent of the δ¹⁸O of water and δ¹³C of DIC from which carbonate grew. Thus, this technique can be applied to parts of the geological record where the stable isotope compositions of waters are unknown. Moreover, simultaneous determinations of Δ₄₇ and δ¹⁸O for carbonates will constrain the δ¹⁸O of water from which they grew.     

Carbonate clumped isotope thermometry of deep-sea corals and implications for vital effects

Here we calibrate the carbonate clumped isotope thermometer in modern deep-sea corals. We examined 11 specimens of three species of deep-sea corals and one species of a surface coral spanning a total range in growth temperature of 2-25 °C. External standard errors for individual measurements ranged from 0.005‰ to 0.011‰ (average: 0.0074‰) which corresponds to ∼1-2 °C. External standard errors for replicate measurements of Δ₄₇ in corals ranged from 0.002‰ to 0.014‰ (average: 0.0072‰) which corresponds to 0.4-2.8 °C. We find that skeletal carbonate from deep-sea corals shows the same relationship of Δ₄₇ (the measure of ¹³C-¹⁸O ordering) to temperature as does inorganic calcite. In contrast, the δ¹³ C and δ¹⁸O values of these carbonates (measured simultaneously with Δ₄₇ for every sample) differ markedly from equilibrium with seawater; i.e., these samples exhibit pronounced ‘vital effects’ in their bulk isotopic compositions. We explore several reasons why the clumped isotope compositions of deep-sea coral skeletons exhibit no evidence of a vital effect despite having large conventional isotopic vital effects.     

An Isotope Dilution ICP‐MS Method for the Determination of Mg/Ca and Sr/Ca Ratios in Calcium Carbonate

Mg/Ca and Sr/Ca ratios in calcium carbonate are important components of many palaeoclimate studies. We present an isotope dilution method relying on a single mixed spike containing ²⁵Mg, ⁴³Ca and ⁸⁷Sr. Dozens of samples per day, as small as 10 μg of carbonate, could be dissolved, spiked and run in an ICP‐MS with a precision of 0.8% (2 RSD). Two instruments types, a sector field and a quadrupole ICP‐MS, were compared. The best long term precision found was 0.4% (2 RSD), although this increased by up to a factor of two when samples of very different Mg or Sr content were run together in the same sequence. Long term averages for the two instruments concurred. No matrix effects were detected for a range of Ca concentrations between 0.2 and 2 mmol l^‐1. Accuracy, tested by measuring synthetic standard solutions, was 0.8% with some systematic trends. We demonstrate the strength of this isotope dilution method for (a) obtaining accurate results for sample sets that present a broad Mg and Sr range and (b) testing solid carbonates as candidate reference materials for interlaboratory consistency. Mg/Ca and Sr/Ca results for reference materials were in good agreement with values from the literature.     

“The Coast” is Complicated: A Model to Consistently Describe the Nation’s Coastal Population

Our nation’s coast is a complicated management area where no single delineation provides all of the demographic statistics needed to address the full range of policy and management issues. As a result, several different coastal delineations are currently being used, yielding a variety of US coastal population statistics. This paper proposes a simple model for generating and applying coastal population statistics at the national and regional level to increase consistency in coastal policy discussions and improve public understanding of coastal issues. The model includes two major components. The first component is “the population that most directly affects the coast,” represented by the permanent US population that resides in a standard suite of Coastal Watershed Counties, where land use and water quality changes most directly impact coastal ecosystems. The second component is “the population most directly affected by the coast,” represented by the permanent US population that resides in a standard suite of Coastal Shoreline Counties that are directly adjacent to the open ocean, major estuaries, and the Great Lakes, which due to their proximity to these waters, bear a great proportion of the full range of effects from coastal hazards and host the majority of economic production associated with coastal and ocean resources.     

Evaporation and land surface energy budget at the Salar de Atacama, Northern Chile

Playa systems are driven by evaporation processes, yet the mechanisms by which evaporation occurs through playa salt crusts are still poorly understood. In this study we examine playa evaporation as it relates to land surface energy fluxes, salt crust characteristics, groundwater and climate at the Salar de Atacama, a 3000 km² playa in northern Chile containing a uniquely broad range of salt crust types. Land surface energy budget measurements were taken at eight representative sites on this playa during winter (August 2001) and summer (January 2002) seasons. Measured values of net all-wave radiation were highest at vegetated and rough halite crust sites and lowest over smooth, highly reflective salt crusts. Over most of the Salar de Atacama, net radiation was dissipated by means of soil and sensible heat fluxes. Dry salt crusts tended to heat and cool very quickly, whereas soil heating and cooling occurred more gradually at wetter vegetated sites. Sensible heating was strongly linked to wind patterns, with highest sensible heat fluxes occurring on summer days with strong afternoon winds. Very little energy available at the land surface was used to evaporate water. Eddy covariance measurements could only constrain evaporation rates to within 0.1 mm d⁻¹, and some measured evaporation rates were less than this margin of uncertainty. Evaporation rates ranged from 0.1 to 1.1 mm d⁻¹ in smooth salt crusts around the margin of the salar and from 0.4 to 2.8 mm d⁻¹ in vegetated areas. No evaporation was detected from the rugged halite salt crust that covers the interior of the salar, though the depth to groundwater is less than 1 m in this area. These crusts therefore represent a previously unrecorded end member condition in which the salt crusts form a practically impermeable barrier to evaporation.     

A statistical study of active regions 1967–1981

We have studied 15 years of active region data based on the Mount Wilson daily magnetograms in the interval 1967–1981. The analysis revealed the following: (1) The integral number of regions decreases exponentially with increasing region sizes, or N(A) = 4788 exp(-A/175) for the 15 years of data, where A is the area in square degrees and N(A) is the number of active regions with area A. (2) The average area of active regions varies with the phase of the solar cycle. There are more larger regions during maximum than during minimum. (3) Regions in the north are 10% larger on average than those in the south during this interval. This coincides with a similar asymmetry in the total magnetic flux between the hemispheres. (4) Regions of all sizes and magnetic complexities show the same characteristic latitude variation with phase in the solar cycle. The largest regions, however, show a narrower latitude range.     

Some factors controlling the concentration of small ions near the ground

Summary During continuous measurements of the concentration of small ions near the ground made over the period of many months, several causes of variation were identified. During rain in large electric fields, ions of sign opposite to that of the potential gradient were produced in sufficiently large numbers to give rise to very high concentrations over short periods. Sometimes, after rain, a considerable increase in the density of small ions was found, suggesting a reduction in the numbers of nuclei and large ions. In moderate electric fields, a reduction was observed in the concentration of ions of sign opposite to that of the potential gradient in a way corresponding to the electrode effect. A simplified theory of the effect predicts results similar to those found in practice.The paper will appear elsewhere.