Temporal Variations in the Dissolved Nutrient Stocks in the Surface Water of the Western North Atlantic Ocean

Changes in patterns of undetectability and molar ratios of dissolved nutrients in the euphotic zone of the oligotrophic western North Atlantic Ocean were investigated utilizing the Bermuda Atlantic Time-series Study (BATS) data set of the US Joint Global Ocean Flux Study (JGOFS). Our aim was to examine the temporal dynamics of nutrient stocks over a decade (1989∼1998) and to gain insight into the interactions between the different biotic and abiotic factors underlying BATS. Patterns of nutrient undetectability clearly revealed the depleted nature of the nutrients in surface water at the BATS location, particularly phosphorous. The N:P ratio was consistently far above the nominal Redfield ratio (mean, 38.5) but was significantly lower during the 1993∼1994 period (22.1). Over the same period the proportion of samples depleted in N only increased while the proportion of samples depleted in P only decreased. This indicates an overall reduction of N relative to P in the surface water at BATS during the 1993∼1994 period, the reasons for this anomaly, though, are not clear. The correlation analysis between the biotic and abiotic variables at BATS has indicated some interesting relationships that can help understand some of the parameters affecting nutrient stocks in the euphotic zone and their consequent impacts on marine biota. Although nutrient stocks in the oligotrophic environment are limited, they might be subject to interannual variation that may become anomalous in some cases. These variations might underlay significant feedback mechanisms by affecting marine productivity, the prime factor controlling the sequestration of atmospheric CO₂ by the oceans. This revised version was published online in July 2006 with corrections to the Cover Date.     

Fixation of CO2 by chrysotile in low-pressure dry and moist carbonation: Ex-situ and in-situ characterizations

A detailed study of low-pressure gas-solid carbonation of chrysotile in dry and humid environments has been carried out. The evolving structure of chrysotile and its reactivity as a function of temperature (300-1200 °C), humidity (0-10 mol %) and CO₂ partial pressure (20-67 mol %), thermal preconditioning, and alkali metal doping (Li, Na, K, Cs) have been monitored through in-situ X-ray photoelectron spectroscopy, isothermal thermogravimetry/mass spectrometry, ex-situ X-ray powder diffraction, and water and nitrogen adsorption/desorption. Based on chrysotile crystalline structure and its nanofibrilar orderliness, a multistep carbonation mechanism was elaborated to explain the role of water during chrysotile partial amorphisation, formation of periclase, brucite, and hydromagnesite crystalline phases, and surface passivation thereof, during humid carbonation. The weak carbonation reactivity was rationalized in terms of incongruent CO₂ van der Waals molecular diameters with the octahedral-tetrahedral lattice constants of chrysotile. This lack of reactivity appeared to be relatively indifferent to the facilitated water crisscrossing during chrysotile core dehydroxylation/pseudo-amorphisation and surface hydroxylation induced product stabilization during humid carbonation. Thermodynamic stability domains of the species observed at low pressure have been thoroughly discussed on the basis of X-ray powder diffraction patterns and X-ray photoelectron spectroscopy evidence. The highest carbon dioxide uptake occurred at 375 °C in moist atmospheres. On the basis of chrysotile fresh N₂ BET area, nearly 15 atoms out of 100 of the surface chrysotile brucitic Mg moiety have been carbonated at this temperature which was tantamount to the carbonation of about 2.5 at. % of the total brucitic Mg moiety in chrysotile. The carbonation of brucite (Mg(OH)₂) impurities coexisting in chrysotile was minor and estimated to contribute by less than 17.6 at. % of the total converted magnesium. The presence of cesium traces (3 Cs atoms per 100 Mg atoms) was found to boost chrysotile carbonation capacity by a factor 2.7.