δC of low-molecular-weight organic acids generated by the hydrous pyrolysis of oil-prone source rocks

Low-molecular-weight (LMW) aqueous organic acids were generated from six oil-prone source rocks under hydrous-pyrolysis conditions. Differences in total organic carbon-normalized acid generation are a function of the initial thermal maturity of the source rock and the oxygen content of the kerogen (OI). Carbon-isotope analyses were used to identify potential generation mechanisms and other chemical reactions that might influence the occurrence of LMW organic acids. The generated LMW acids display increasing ¹³C content as a function of decreasing molecular weight and increasing thermal maturity. The magnitudes of observed isotope fractionations are source-rock dependent. These data are consistent with δ¹³C values of organic acids presented in a field study of the San Joaquin Basin and likely reflect the contributions from alkyl-carbons and carboxyl-carbons with distinct δ¹³C values. The data do not support any particular organic acid generation mechanism. The isotopic trends observed as a function of molecular weight, thermal maturity, and rock type are not supported by either generation mechanisms or destructive decarboxylation. It is therefore proposed that organic acids experience isotopic fractionation during generation consistent with a primary kinetic isotope effect and subsequently undergo an exchange reaction between the carboxyl carbon and dissolved inorganic carbon that significantly influences the carbon isotope composition observed for the entire molecule. Although generation and decarboxylation may influence the δ¹³C values of organic acids, in the hydrous pyrolysis system described, the nondestructive, pH-dependent exchange of carboxyl carbon with inorganic carbon appears to be the most important reaction mechanism controlling the δ¹³C values of the organic acids.     

Generation of mid-ocean ridge basalts at pressures from 1 to 7 GPa

We propose a model for the generation of average MORBs based on phase relations in the CaO-MgO-Al₂O₃-SiO₂-CO₂ system at pressures from 3 to 7 GPa and in the CaO-MgO-Al₂O₃-SiO₂-Na₂O-FeO (CMASNF) system at pressures from ∼0.9 to 1.5 GPa. The MELT seismic tomography (Forsyth et al., 2000) across the East Pacific Rise shows the largest amount of melt centered at ∼30-km depth and lesser amounts at greater depths. An average mantle adiabat with a model-system potential temperature (T_p) of 1310°C is used that is consistent with this result. In the mantle, additional minor components would lower solidus temperatures ∼50°C, which would lower T_p of the adiabat for average MORBs to ∼1260°C. The model involves generation of carbonatitic melts and melts that are transitional between carbonatite and kimberlite at very small melt fractions (<0.2%) in the low-velocity zone at pressures of ∼2.6 to 7 GPa in the CMAS-CO₂ system, roughly the pressure range of the PREM low-velocity zone. These small-volume, low-viscosity melts are mixed with much larger volumes of basaltic melt generated at the plagioclase-spinel lherzolite transition in the pressure range of ∼0.9 to 1.5 GPa.In this model, solidus phase relations in the pressure range of the plagioclase-spinel lherzolite transition strongly, but not totally, control the major-element characteristics of MORBs. Although the plagioclase-spinel lherzolite transition suppresses isentropic decompression melting in the CMAS system, this effect does not occur in the topologically different and petrologically more realistic CMASNF system. On the basis of the absence of plagioclase from most abyssal peridotites, which are the presumed residues of MORB generation, we calculate melt productivity during polybaric fractional melting in the plagioclase-spinel lherzolite transition interval at exhaustion of plagioclase in the residue. In the CMASN system, these calculations indicate that the total melt productivity is ∼24%, which is adequate to produce the oceanic crust. The residual mineral proportions from this calculation closely match those of average abyssal peridotites.Melts generated in the plagioclase-spinel lherzolite transition are compositionally distinct from all MORB glasses, but do not have a significant fractional crystallization trend controlled by olivine alone. They reach the composition field of erupted MORBs mainly by crystallization of both plagioclase and olivine, with initial crystallization of either one of these phases rapidly joined by the other. This is consistent with phenocryst assemblages and experimental studies of the most primitive MORBs, which do not show an olivine-controlled fractionation trend. The model is most robust for the eastern Pacific, where an adiabat with a T_p of ∼1260°C is supported by the MELT seismic data and where the global inverse correlation of (FeO)₈ with (Na₂O)₈ is weak. Average MORBs worldwide also are well modeled. A heterogeneous mantle consisting of peridotite of varying degrees of major-element depletion combined with phase-equilibrium controls in the plagioclase-spinel lherzolite transition interval would produce the form of the global correlations at a constant T_p, which suggests a modest range of T_p along ridges. Phase-composition data for the CMASNF system are presently not adequate for quantitative calculation of (FeO)₈-(Na₂O)₈-(CaO/Al₂O₃)₈ systematics in terms of this model. The near absence of basalts in the central portion of the Gakkel Ridge suggests a lower bound for T_p along ridges of ∼1240°C, a potential temperature just low enough to miss the solidus for basalt production at ∼0.9 GPa. An upper bound for T_p is poorly constrained, but the complete absence of picritic glasses in Iceland and the global ridge system suggests an upper bound of ∼1400°C. In contrast to some previous models for MORB generation that emphasize large potential temperature variations in a relatively homogeneous peridotitic mantle, our model emphasizes modest potential temperature variations in a peridotitic mantle that shows varying degrees of heterogeneity. Calculations indicate that melt productivity changes from 0 to 24% for a change in T_p from 1240 to 1260°C, effectively producing a rapid increase to full crustal thickness or decrease to none as ridges appear and disappear.     

Possible implications of modal mineralogy for melting in mantle lherzolites

The melting reaction at the solidus of mantle peridotite is commonly peritectic in nature, with liquid and one or more solid phases produced upon melting. In some situations, one of the phases participating on the reactant side of the reaction is present in low abundance. This article explores the possible effects of the low abundance of a reactant phase on the melting behavior of mantle peridotite.For example, spinel lherzolite begins to melt via the peritectic reaction, clinopyroxene + orthopyroxene + spinel = olivine + liquid in the ∼1- to 2-GPa pressure range. In natural spinel lherzolites, spinel is a modally minor mineral and may be infrequently in contact with both clinopyroxene and orthopyroxene. If these mutual contacts are insufficient to generate an interconnected melt, then significant melting may not occur until a combination of minerals that are modally abundant and in contact begin to melt. This scenario could have implications for the physical process of melting and for the timing of formation of an interconnected melt network and separation of the melt from the residue.To begin to investigate this possibility, the spatial relationships between the constituent minerals in two fertile spinel lherzolites were determined by elemental mapping with the electron microprobe. Olivine, orthopyroxene, and clinopyroxene are of similar size, whereas the spinel was smaller and interstitial. Spinel and clinopyroxene are frequently in contact, but mutual contacts of spinel, clinopyroxene, and orthopyroxene are rare. Because of the changes in modal mineralogy anticipated for these lherzolites with increasing temperature, these mutual contacts will be even less common at the solidus. Therefore, an interconnected, potentially extractable, melt may not occur by the solidus spinel + orthopyroxene + clinopyroxene melting reaction.     

Climate change impacts on U.S. Coastal and Marine Ecosystems

Increases in concentrations of greenhouse gases projected for the 21st century are expected to lead to increased mean global air and ocean temperatures. The National Assessment of Potential Consequences of Climate Variability and Change (NAST 2001) was based on a series of regional and sector assessments. This paper is a summary of the coastal and marine resources sector review of potential impacts on shorelines, estuaries, coastal wetlands, coral reefs, and ocean margin ecosystems. The assessment considered the impacts of several key drivers of climate change: sea level change; alterations in precipitation patterns and subsequent delivery of freshwater, nutrients, and sediment; increased ocean temperature; alterations in circulation patterns; changes in frequency and intensity of coastal storms; and increased levels of atmospheric CO₂. Increasing rates of sea-level rise and intensity and frequency of coastal storms and hurricanes over the next decades will increase threats to shorelines, wetlands, and coastal development. Estuarine productivity will change in response to alteration in the timing and amount of freshwater, nutrients, and sediment delivery. Higher water temperatures and changes in freshwater delivery will alter estuarine stratification, residence time, and eutrophication. Increased ocean temperatures are expected to increase coral bleaching and higher CO₂ levels may reduce coral calcification, making it more difficult for corals to recover from other disturbances, and inhibiting poleward shifts. Ocean warming is expected to cause poleward shifts in the ranges of many other organisms, including commercial species, and these shifts may have secondary effects on their predators and prey. Although these potential impacts of climate change and variability will vary from system to system, it is important to recognize that they will be superimposed upon, and in many cases intensify, other ecosystem stresses (pollution, harvesting, habitat destruction, invasive species, land and resource use, extreme natural events), which may lead to more significant consequences.     

A Comparison of Two-Phase Dynamic Upscaling Methods Based on Fluid Potentials

Although a number of methods for calculating dynamic pseudo-functions have been developed over the years, there is still a lack of understanding as to why a certain method will succeed in some cases but fail in others. In this paper, we describe the results of an assessment of several upscaling methods, namely the Kyte and Berry (KB) method, the Stone method, the Hewett and Archer (HA) method and the Transmissibility-Weighted (TW) method. We have analyzed the equations for deriving the methods and investigated the results of numerical simulations of gas displacing oil, in a variety of models to enable us to gain new insights into these, and related, upscaling methods. In particular, some novel observations on methods based on fluid potential are presented and the issue of using predicted fluid mobilities as a criterion of accuracy of an upscaling method is clarified.     

Inorganic speciation of dissolved elements in seawater: the influence of pH on concentration ratios

Assessments of inorganic elemental speciation in seawater span the past four decades. Experimentation, compilation and critical review of equilibrium data over the past forty years have, in particular, considerably improved our understanding of cation hydrolysis and the complexation of cations by carbonate ions in solution. Through experimental investigations and critical evaluation it is now known that more than forty elements have seawater speciation schemes that are strongly influenced by pH. In the present work, the speciation of the elements in seawater is summarized in a manner that highlights the significance of pH variations. For elements that have pH-dependent species concentration ratios, this work summarizes equilibrium data (S = 35, t = 25°C) that can be used to assess regions of dominance and relative species concentrations. Concentration ratios of complex species are expressed in the form log[A]/[B] = pH - C where brackets denote species concentrations in solution, A and B are species important at higher (A) and lower (B) solution pH, and C is a constant dependent on salinity, temperature and pressure. In the case of equilibria involving complex oxy-anions (MO _x (OH) _y ) or hydroxy complexes (M(OH) _n ), C is written as pK _n = -log K _n or pK _n * = -log K _n * respectively, where K _n and K _n * are equilibrium constants. For equilibria involving carbonate complexation, the constant C is written as pQ = -log(K ₂ ^l K _n [HCO₃ ^-]) where K ₂ ^l is the HCO₃ ^- dissociation constant, K _n is a cation complexation constant and [HCO₃ ^-] is approximated as 1.9 × 10^-3 molar. Equilibrium data expressed in this manner clearly show dominant species transitions, ranges of dominance, and relative concentrations at any pH.