Overstepping the garnet isograd: a comparison of QuiG barometry and thermodynamic modeling

The consequences of overstepping the garnet isograd reaction have been investigated by comparing the composition of garnet formed at overstepped P–T conditions (the overstep or “OS” model) with the P–T conditions that would be inferred by assuming garnet nucleated in equilibrium with the matrix assemblage at the isograd (the equilibrium or “EQ” model). The garnet nucleus composition formed at overstepped conditions is calculated as the composition that produces the maximum decrease in Gibbs free energy from the equilibrated, garnet-absent, matrix assemblage for the bulk composition under study. Isopleths were then calculated for this garnet nucleus composition assuming equilibrium with the matrix assemblage (the EQ model). Comparison of the actual P–T conditions of nucleation (the OS model) with those inferred from the EQ model reveals considerable discrepancy between the two. In general, the inferred garnet nucleation P–T conditions (the EQ model) are at a lower temperature and higher or lower pressure (depending on the coexisting calcic phase(s)) than the actual (OS model) nucleation conditions. Moreover, the degree of discrepancy increases with the degree of overstepping. Independent estimates of the pressure of nucleation of garnet were made using the Raman shift of quartz inclusions in garnet (quartz-in-garnet or QuiG barometry). To test the validity of this method, an experimental synthesis of garnet containing quartz inclusions was made at 800 °C, 20 kbar, and the measured Raman shift reproduced the synthesis conditions to within 120 bars. Raman band shifts from three natural samples were then used to calculate an isochore along which garnet was presumed to have nucleated. Model calculations were made at several temperatures along this isochore (the OS model), and these P–T conditions were compared to those computed assuming equilibrium nucleation (the EQ model) to estimate the degree of overstepping displayed by these samples. A sample from the garnet isograd in eastern Vermont is consistent with overstepping of around 10 degrees and 0.6 kbar (affinities of around 2 kJ/mole garnet). A sample from the staurolite–kyanite zone in the same terrane requires overstepping of around 50 °C and 2–5 kbar (affinities of around 10–18 kJ/mole garnet). A similar amount of overstepping was inferred for a blueschist sample from Sifnos, Greece. These results indicate that overstepping of garnet nucleation reactions may be common and pronounced in regionally metamorphosed terranes, and that the P–T conditions and paths inferred from garnet zoning studies may be egregiously in error.     

Calcium,Na, K and Mg Concentrations in Seawater by Inductively Coupled Plasma‐Atomic Emission Spectrometry: Applications to IAPSO Seawater Reference Material,Hydrothermal Fluids and Synthetic Seawater Solutions

We report a measurement procedure to determine simultaneously the major cation concentrations (Na, Ca, K and Mg) of seawater‐derived solutions by inductively coupled plasma‐atomic emission spectrometry. The best results were obtained when the IAPSO (‘standard’) seawater reference material was diluted by thirty times with Milli‐Q^® water. We obtained an average reference value r_K (the ratio of the mass fraction of potassium to that of chlorine, i.e., (g kg^?1)/(g kg^?1)) for IAPSO seawater of 0.0205 ± 0.0006 (2.9% RSD), not significantly different from 0.0206 ± 0.0005 (2.4% RSD) for seawater composition reported in the literature. The measured Na, Ca and Mg concentrations correspond to r_Na, r_Ca and r_Mg values of 0.5406 ± 0.0026 (0.5% RSD), 0.02192 ± 0.00048 (2.2% RSD) and 0.06830 ± 0.00047 (0.7% RSD), respectively, in line with previous values measured by wet‐chemistry and atomic absorption spectrophotometry or wet‐chemical titration. Our measurement procedure was used successfully on synthetic seawater solutions and high‐temperature hydrothermal fluids.     

Weighting of Observed Heads for the Inverse Problem

In using least-squares parameter estimation techniques to solve for hydrogeologic parameters, one may use a weighting function to reflect differing reliabilities of head measurements. In studies published to date, the weighting function has been used in an ad boc manner or not at all. The inverse square of the observed hydraulic gradient, adjusted to reflect the modeler's perception of geologic heterogeneity and data reliability, is typically an appropriate weighting function.     

Glycol Ethers As Groundwater Contaminants

Ether derivatives of dihydroxy alcohols, which are formed from ethylene or propylene, comprise an important group of groundwater contaminants known as glycol ethers. Compounds in this group are used as solvents, cleaning agents, and emulsifiers in many chemical products and manufacturing operations. Glycol ethers have been associated with a variety of toxic effects, and some compounds in the group are relatively potent teratogens. The limited information available suggests that glycol ethers are contaminants in groundwater, especially in anaerobic plumes emanating from disposal of mixed industrial and household waste. Most methods used to analyze groundwater samples cannot adequately detect 7g/’ (ppb) concentrations of glycol ethers, and the existing methods perform worst for the most widely used and toxic species. A new method capable of analyzing 7g/’ concentrations of glycol ethers was recently developed, and its use is recommended for groundwater samples where glycol ethers are likely to be present. Résumé. Les éthers glycol, polluants des eaux souterraines. Les dérivés d'éther de dihydroxy-alcool, formés à partir de l'éthylène ou du propylène, constituent un important groupe de polluants des eaux souterraines connus sous le nom d'éthers glycol. Les composés de ce groupe sont utilisés comme solvants, comme agents de nettoyage et comme émulsifiants dans de nombreux produits chimiques et dans de nombreux processus de fabrication. Des effets toxiques variés ont été attribués aux éthers glycol et certains des composés sont des agents tératogènes relativement puissants. Les données disponibles, qui sont limitées, indiquent que les éthers glycol sont des polluants communs dans les eaux souterraines, particulièrement dans les panaches anaéorobies émis par les décharges mixtes de déchets industriels et domestiques. La plupart des méthodes d'analyse d'échantillons d'eau souterraine ne sont pas capables de détecter convenablement des concentrations en éthers glycol de l'ordre du 7g/l (ppb); les méthodes actuelles sont médiocres pour doser les espèces toxiques les plus courantes. Une nouvelle méthode permettant de doser des concentrations en éthers glycol de l'ordre du 7 g/l a été récemment mise au point; son utilisation est préconisée pour les échantillons d'eau souterraine contenant des éthers glycol.     

Coupled redox transformations of catechol and cerium at the surface of a cerium(III) phosphate mineral

Highly insoluble Ce-bearing phosphate minerals form by weathering of apatite [Ca₅(PO₄)₃.(OH,F,Cl)], and are important phosphorous repositories in soils. Although these phases can be dissolved via biologically-mediated pathways, the dissolution mechanisms are poorly understood. In this paper we report spectroscopic evidence to support coupling of redox transformations of organic carbon and cerium during the reaction of rhabdophane (CePO₄·H₂O) and catechol, a ubiquitous biogenic compound, at pH 5. Results show that the oxic–anoxic conditions influence the mineral dissolution behavior. Under anoxic conditions, the release of P and Ce occurs stoichiometrically. In contrast, under oxic conditions, the mineral dissolution behavior is incongruent, with dissolving Ce³⁺ ions oxidizing to CeO₂. Reaction product analysis shows the formation of CO₂, polymeric C, and oxalate and malate. The presence of more complex forms of organic carbon was also confirmed. Near edge X-ray absorption fine structure spectroscopy measurements at Ce-M_4,5 and C-K absorption edges on reacted CePO₄·H₂O samples in the absence or presence of catechol and dissolved oxygen confirm that (1) the mineral surface converts to the oxide during this reaction, while full oxidation is limited to the near-surface region only; (2) the Ce valence remains unchanged when the reaction between CePO₄·H₂O and O₂ but in the absence of catechol. Carbon K-edge spectra acquired from rhabdophane reacted with catechol under oxic conditions show spectral features before and after reaction that are considerably different from catechol, indicating the formation of more complex organic molecules. Decreases in intensity of characteristic catechol peaks are accompanied by the appearance of new π^* resonances due to carbon in carboxyl (ca. 288.5 eV) and carbonyl (ca. 289.3 eV) groups, and the development of broad structure in the σ^* region characteristic of aliphatic carbon. Evolution of the C K-edge spectra is consistent with aromatic-ring cleavage and polymerization. These results further substantiate that the presence of catechol, O₂ (aq) causes both the oxidation of structural Ce³⁺ and the transformation of catechol to more complex organic molecules. Scanning Transmission X-Ray Microscopy measurements at the C K and Ce M_4,5 edges indicate three dominant organic species, varying in complexity and association with the inorganic phase. Untransformed catechol is loosely associated with CeO₂, whereas more complex organic molecules that exhibit lower aromaticity and stronger CO π^* resonances of carboxyl-C and carbonyl-C groups are only found in association with the grains. These results further serve as basis to postulate that, in the presence of O₂, CeO₂ can mediate the oxidative polymerization of catechol to form higher molecular weight polymers. The present work provides evidence for a pathway of biologically-induced, non-enzymatic oxidation of cerium and formation of small CeO₂ particles at room temperature. These findings may have implications for carbon cycling in natural and cerium-contaminated soils and aqueous environments.     

Sedimentary evidence of deglacial megafloods in the northern Gulf of Mexico (Pigmy Basin)

Cored sediments from the Pigmy Basin, northern Gulf of Mexico, were analyzed in order to better constrain late deglacial and early Holocene paleoenvironmental and sedimentary changes in response to North American climate evolution. Mineralogical and geochemical proxies indicate the succession of two sedimentary regimes: dominantly detrital during the deglaciation (15–12.9 cal ka BP) whereas biogenic contribution relatively increased later on during the Younger Dryas and early Holocene (12.9 and 10 cal ka BP). Geochemical data reveal that the deglacial record mainly reflects variations of terrigenous supply via the Mississippi River rather than modifications of redox conditions in the basin. Specific variations of almost all the parameters measured in this paper are synchronous with the main deglacial meltwater episode (Meltwater Spike) described or modeled in previous marine or continental studies. During this episode, most parameters display “stair-step-like” – pattern variations highlighting three successive steps within the main meltwater flow. Variations in grain-size and clay mineral assemblage recorded in the Pigmy Basin indicate that the erosional regime was very strong on land during the first part of the Meltwater Spike, and then milder, inducing more subtle modifications in the sedimentary regime in this part of the Gulf. Specific geochemical and mineralogical signatures (notably, clay minerals and trace metal geochemistry) pinpoint a dominant origin from NW North America for detrital particles reflecting meltwater outflow from the south-western Laurentide Ice Sheet (LIS) margin during the most intense freshwater discharge. The observed decrease of the sedimentation rate from about 200 to 25 cm/ka at ca 12.9 ka evidenced a drastic decrease of erosional processes during late phase of discharge, consistently with the hypotheses of major reduction of meltwater flow. The major modification at 12.9 cal ka BP is interpreted to result from both modifications of the main Mississippi fluvial regime due to eastward and northward rerouting of meltwater flow at the onset of the Younger Dryas, and the increase of sea-surface temperature linked to insolation. Finally, slight grain-size modifications suggest that some freshwater discharges may have episodically reached the Gulf of Mexico after the Younger Dryas reflecting possible small adjustments of the postglacial hydrological regime.     

Sea-level rise research and dialogue in North Carolina: Creating windows for policy change

Coastal areas are among the world's most vulnerable landscapes to impacts related to climate change, including inundation from sea-level rise (SLR), increased exposure to shoreline erosion, and greater frequency and intensity of storms. The status of research on the physical, ecological, and socio-economic effects of vulnerability to SLR and progress toward planning for its consequences varies from region to region worldwide. Here, we synthesize the results of three decades of SLR research and the development of coastal management policies in North Carolina, USA. We identify the major factors responsible for opening new policy ‘windows’ that address SLR, including how stakeholders have developed an increased understanding of the risks, the extent of public dialogue about potential response strategies, and advances in political receptivity to policy change. Research and policy progress in North Carolina continue to provide a model for other regions to help guide and evaluate the development of coastal policies.