A closer look at arrested spinodal decomposition in protein solutions

Concentrated aqueous solutions of the protein lysozyme undergo a liquid solid transition upon a temperature quench into the unstable spinodal region below a characteristic arrest temperature of Tf=15C. We use video microscopy and ultra-small angle light scattering in order to investigate the arrested structures as a function of initial concentration, quench temperature and rate of the temperature quench. We find that the solid-like samples show all the features of a bicontinuous network that is formed through an arrested spinodal decomposition process. We determine the correlation length Xi and demonstrate that Xi exhibits a temperature dependence that closely follows the critical scaling expected for density fluctuations during the early stages of spinodal decomposition. These findings are in agreement with an arrest scenario based on a state diagram where the arrest or gel line extends far into the unstable region below the spinodal line. Arrest then occurs when during the early stage of spinodal decomposition the volume fraction phi2 of the dense phase intersects the dynamical arrest threshold phi2Glass, upon which phase separation gets pinned into a space-spanning gel network with a characteristic length Xi

A global algorithm for estimating Absolute Salinity

The International Thermodynamic Equation of Seawater – 2010 has defined the thermodynamic properties of seawater in terms of a new salinity variable, Absolute Salinity, which takes into account the spatial variation of the composition of seawater. Absolute Salinity more accurately reflects the effects of the dissolved material in seawater on the thermodynamic properties (particularly density) than does Practical Salinity. <br><br> When a seawater sample has standard composition (i.e. the ratios of the constituents of sea salt are the same as those of surface water of the North Atlantic), Practical Salinity can be used to accurately evaluate the thermodynamic properties of seawater. When seawater is not of standard composition, Practical Salinity alone is not sufficient and the Absolute Salinity Anomaly needs to be estimated; this anomaly is as large as 0.025 g kg<sup>−1</sup> in the northernmost North Pacific. Here we provide an algorithm for estimating Absolute Salinity Anomaly for any location (<i>x, y, p</i>) in the world ocean. <br><br> To develop this algorithm, we used the Absolute Salinity Anomaly that is found by comparing the density calculated from Practical Salinity to the density measured in the laboratory. These estimates of Absolute Salinity Anomaly however are limited to the number of available observations (namely 811). In order to provide a practical method that can be used at any location in the world ocean, we take advantage of approximate relationships between Absolute Salinity Anomaly and silicate concentrations (which are available globally)

The effects of biogeochemical processes on oceanic conductivity/salinity/density relationships and the characterization of real seawater

As seawater circulates through the global ocean, its relative composition undergoes small variations. This results in changes to the conductivity/salinity/density relationship, which is currently well-defined only for Standard Seawater obtained from a particular area in the North Atlantic. These changes are investigated here by analysis of laboratory experiments in which salts are added to seawater, by analysis of oceanic observations of density and composition anomalies, and by mathematical investigation using a model relating composition, conductivity, and density of arbitrary seawaters. Mathematical analysis shows that understanding and describing the effect of changes in relative composition on operational estimates of salinity using the Practical Salinity Scale 1978 and on density using an equation of state for Standard Seawater require the use of a number of different salinity variables and a family of haline contraction coefficients. These salinity variables include an absolute salinity <i>S</i><sub>A</sub><sup>soln</sup>, a density salinity <i>S</i><sub>A</sub><sup>dens</sup>, the reference salinity <i>S</i><sub>R</sub>, and an added-mass salinity <i>S</i><sub>A</sub><sup>add</sup>. In addition, a new salinity variable <i>S</i><sub>∗</sub> is defined, which represents the preformed salinity of a Standard Seawater component to which biogeochemical processes add material. In spite of this complexity, observed correlations between different ocean biogeochemical processes allow the creation of simple formulas that can be used to convert between the different salinity and density measures, allowing for the operational reduction of routine oceanographic observations

The Characteristics and Biological Relevance of Inorganic Amorphous Calcium Carbonate (ACC) Precipitated from Seawater

The importance of amorphous calcium carbonate (ACC) as a precursor phase in the biomineralization of marine calcifiers is increasingly being reported, particularly as the presence of ACC has been observed or inferred in several major groups. Here, we investigate the structure of ACC and the conditions required for its precipitation from seawater-based solutions, with an emphasis on the coinfluence of the carbonate system (pH, dissolved inorganic carbon (DIC) concentration), seawater Mg/Ca ratio, and presence of amino acids. We find that Mg2+ and the presence of aspartic acid, glutamic acid, and glycine strongly inhibit ACC precipitation. Moreover, we were unable to precipitate ACC from seawater with a carbonate chemistry within the range of that thought to characterize the calcification site of certain marine calcifiers (i.e., DIC < 6 mM, pH < 9.3), although substantial modification of the seawater Mg/Ca ratio (Mg/Casw) allowed precipitation at a reduced DIC with the implication that this could be an important component of utilizing an ACC pathway. In addition, the degree to which Mg/Casw and the presence of amino acids influences the structure of ACC and the necessary seawater [CO3 2-] for precipitation is strongly pH dependent. At lower, more biologically relevant pH than that typical of much inorganic work, decreasing Mg/Casw can result in greater long-range order and less water of crystallization but facilitates precipitation at a considerably lower [CO3 2-] than at higher pH

Differential sound velocity apparatus for the investigation of protein solutions

A differential method for the measurement of sound velocity in solutions is described. The instrument uses two identical acoustic resonators and a newly developed electronic measuring system. The sound velocity is determined with a relative accuracy of ≈3×10-6 over the entire frequency range 0.5-10 MHz. The instrument has been used to determine the compressibility of protein solutions and to study their velocity dispersion

Ongoing transients in carbonate compensation

Uptake of anthropogenic CO2 is acidifying the oceans. Over the next 2000 years, this will modify the dissolution and preservation of sedimentary carbonate. By coupling new formulas for the positions of the calcite saturation horizon, zsat, the compensation depth, zcc, and the snowline, zsnow, to a biogeochemical model of the oceanic carbonate system, we evaluate how these horizons will change with ongoing ocean acidification. Our model is an extended Havardton-Bear-type box model, which includes novel kinetic descriptions for carbonate dissolution above, between, and below these critical depths. In the preindustrial ocean, zsat and zcc are at 3939 and 4750 m, respectively. When forced with the IS92a CO2 emission scenario, the model forecasts (1) that zsat will rise rapidly (“runaway” conditions) so that all deep water becomes undersaturated, (2) that zcc will also rise and over 1000 years will pass before it will be stabilized by the dissolution of previously deposited CaCO3, and (3) that zsnow will respond slowly to acidification, rising by ∼1150 m during a 2000 year timeframe. A further simplified model that equates the compensation and saturation depths produces quantitatively different results. Finally, additional feedbacks due to acidification on calcification and increased atmospheric CO2 on organic matter productivity strongly affect the positions of the compensation horizons and their dynamics.

Spectrophotometric Calibration of pH Electrodes in Seawater Using Purified m-Cresol Purple

This work examines the use of purified meta-cresol purple (mCP) for direct spectrophotometric calibration of glass pH electrodes in seawater. The procedures used in this investigation allow for simple, inexpensive electrode calibrations over salinities of 20–40 and temperatures of 278.15–308.15 K without preparation of synthetic Tris seawater buffers. The optimal pH range is ∼7.0–8.1. Spectrophotometric calibrations enable straightforward, quantitative distinctions between Nernstian and non-Nernstian electrode behavior. For the electrodes examined in this study, both types of behavior were observed. Furthermore, calibrations performed in natural seawater allow direct determination of the influence of salinity on electrode performance. The procedures developed in this study account for salinity-induced variations in liquid junction potentials that, if not taken into account, would create pH inconsistencies of 0.028 over a 10-unit change in salinity. Spectrophotometric calibration can also be used to expeditiously determine the intercept potential (i.e., the potential corresponding to pH 0) of an electrode that has reliably demonstrated Nernstian behavior. Titrations to ascertain Nernstian behavior and salinity effects can be undertaken relatively infrequently (∼weekly to monthly). One-point determinations of intercept potential should be undertaken frequently (∼daily) to monitor for stable electrode behavior and ensure accurate potentiometric pH determinations

Summer CO2 evasion from streams and rivers in the Kolyma River basin, north-east Siberia

Inland water systems are generally supersaturated in carbon dioxide (CO2) and are increasingly recognized as playing an important role in the global carbon cycle. The Arctic may be particularly important in this respect, given the abundance of inland waters and carbon contained in Arctic soils; however, a lack of trace gas measurements from small streams in the Arctic currently limits this understanding.We investigated the spatial variability of CO2 evasion during the summer low-flow period from streams and rivers in the northern portion of the Kolyma River basin in north-eastern Siberia. To this end, partial pressure of carbon dioxide (pCO2) and gas exchange velocities (k) were measured at a diverse set of streams and rivers to calculate CO2 evasion fluxes. We combined these CO2 evasion estimates with satellite remote sensing and geographic information system techniques to calculate total areal CO2 emissions. Our results show that small streams are substantial sources of atmospheric CO2 owing to high pCO2 and k, despite being a small portion of total inland water surface area. In contrast, large rivers were generally near equilibrium with atmospheric CO2. Extrapolating our findings across the Panteleikha-Ambolikha sub-watersheds demonstrated that small streams play a major role in CO2 evasion, accounting for 86% of the total summer CO2 emissions from inland waters within these two sub-watersheds. Further expansion of these regional CO2 emission estimates across time and space will be critical to accurately quantify and understand the role of Arctic streams and rivers in the global carbon budget

Factors regulating the Great Calcite Belt in the Southern Ocean and its biogeochemical significance

The Great Calcite Belt (GCB) is a region of elevated surface reflectance in the Southern Ocean (SO) covering ~16% of the global ocean and is thought to result from elevated, seasonal concentrations of coccolithophores. Here we describe field observations and experiments from two cruises that crossed the GCB in the Atlantic and Indian sectors of the SO. We confirm the presence of coccolithophores, their coccoliths, and associated optical scattering, located primarily in the region of the subtropical, Agulhas, and Subantarctic frontal regions. Coccolithophore-rich regions were typically associated with high-velocity frontal regions with higher seawater partial pressures of CO2 (pCO2) than the atmosphere, sufficient to reverse the direction of gas exchange to a CO2 source. There was no calcium carbonate (CaCO3) enhancement of particulate organic carbon (POC) export, but there were increased POC transfer efficiencies in high-flux particulate inorganic carbon regions. Contemporaneous observations are synthesized with results of trace-metal incubation experiments, 234Th-based flux estimates, and remotely sensed observations to generate a mandala that summarizes our understanding about the factors that regulate the location of the GCB