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.     

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.     

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.     

Multiple stressors in an estuarine system: Effects of nutrients, trace elements, and trophic complexity on benthic photosynthesis and respiration

The effects of nutrients, trace elements, and trophic complexity on benthic photosynthesis and respriation were studied in the Paxtuxent River estuary near St. Leonard, Maryland. Experiments were conducted over three years (1995–1997) in mesocosms containing riverine sediment and water. The experimental design was 2×2×3 factorial with two levels of nutrients (ambient and + nutrients), two of trace elements (ambient and + trace elements) and three of trophic complexity (plankton, plankton + fish, and plankton + fish + benthos). Trace elements included arsenic (As), copper (Cu), and cadmium (Cd). The experiment was conducted three times in 1995 and 1997 and four times in 1996. In 1995 and 1996, sediments were muddy, while in the final year sediments were sandy. In mesocoms with sandy sediments, nutrient additions increased benthic photosynthesis overall, while trace element additions increased benthic photosynthesis in two of three experimental runs. Benthic photosynthesis in these mesocosms appeared to be related to nitrogen loading. Benthic respiration increased in nutrient and trace element amended mesocosms with sandy sediments, apparently in response to higher benthic photosynthesis. Increasing trophic complexity, particularly the presence of benthic organisms, also increased benthic respiration in mesocosms with sandy sediments. There were no effects of nutrient or trace element additions on benthic photosynthesis and respiration when the sediments were muddy. The lack of consistent responses to nutrient additions was surprising given that benthic respiration rates (and presumably nutrient regeneration) were similar in all three years, regardless of sediment type. Muddy, sediments did not mask, the effects of nutrient addition by supplying more nutrients to benthic microalgae than sandy sediments. In 1996, the presence of filter feeding bivalves increased the relative heterotrophy of sediments, measured as production: respiration. Consistent with increased heterotrophy, effluxes of ammonium and soluble reactive phosphorus from sediments were greater in mesocosms containing benthic organisms. Anthropogenically-induced changes in estuaries, such as loading of nutrients and trace elements or reduced trophic complexity, can have important effects on benthic processes and potentially pelagic processes through feedback mechanisms.     

Determining the trophic guilds of fishes and macroinvertebrates in a seagrass food web

We established trophic guilds of macroinvertebrate and fish taxa using correspondence analysis and a hierarchical clustering strategy for a seagrass food web in winter in the northeastern Gulf of Mexico. To create the diet matrix, we characterized the trophic linkages of macroinvertebrate and fish taxa present inHalodule wrightii seagrass habitat areas within the St. Marks National Wildlife Refuge (Florida) using binary data, combining dietary links obtained from relevant literature for macroinvertebrates with stomach analysis of common fishes collected during January and February of 1994. Heirarchical average-linkage cluster analysis of the 73 taxa of fishes and macroinvertebrates in the diet matrix yielded 14 clusters with diet similarity ≥ 0.60. We then used correspondence analysis with three factors to jointly plot the coordinates of the consumers (identified by cluster membership) and of the 33 food sources. Correspondence analysis served as a visualization tool for assigning each taxon to one of eight trophic guilds: herbivores, detritivores, suspension feeders, omnivores, molluscivores, meiobenthos consumers, macrobenthos consumers and piscivores. These trophic groups, corss-classified with major taxonomic groups, were further used to develop consumer compartments in a network analysis model of carbon flow in this seagrass ecosystem. The method presented here should greatly improve the development of future network models of food webs by providing an objective procedure for aggregating trophic groups.     

Iterative resolution estimation in least‐squares Kirchhoff migration

We apply iterative resolution estimation to least‐squares Kirchhoff migration. Reviewing the theory of iterative optimization uncovers the common origin of different optimization methods. This allows us to reformulate the pseudo‐inverse, model resolution and data resolution operators in terms of effective iterative estimates. When applied to Kirchhoff migration, plots of the diagonal of the model resolution matrix reveal low illumination areas on seismic images and provide information about image uncertainties. Synthetic and real data examples illustrate the proposed technique and confirm the theoretical expectations.     

Rock magnetic evidence of inflation of a flood basalt lava flow

The anisotropy of magnetic susceptibility (AMS) of lava flows is an innovative method which has been proved to be directly related to the shear history of lava. One of the advantages of this method is that it can be used in the absence of other morphological features commonly employed to study the mechanism of emplacement of lava flows. This feature of the AMS method makes it very attractive to gain insight into the mechanism of emplacement of massive, relatively featureless, long lava flows such as those forming flood basalt provinces. In this work, we report the results of the measurement of AMS as a function of vertical position within the Birkett lava flow, one of the Columbia River Basalt Group flows. The observed variation of AMS allows us to identify at least 16 discrete events of lava injection and to estimate the thickness of individual injection events. The AMS-estimated thickness of each injection event (in the range of 0.5-4.0 m) coincides with the range inferred for injected lava pulses in modern Hawaiian lava flows. Thus, the evidence provided by the AMS method supports the notion that at least some flood basalt lava flows were emplaced by the same mechanism as many present-day inflated pahoehoe flows. Regarding the orientation of the principal susceptibilities, in the central part of the flow they define a preferred orientation along an E-W trend, whereas in the outer parts of the flow they have a NNE-SSW trend. This difference in the orientation of the principal susceptibilities is interpreted as the result of a change of flow direction of the lava as emplacement progressed. Electronic supplementary material to this paper can be obtained by using the Springer LINK server located at http://dx.doi.org/10.1007/s00445-002-0203-8.     

Subducted slabs beneath the eastern Indonesia-Tonga region: insights from tomography

Tomographic images of mantle structure beneath the region north and northeast of Australia show a number of anomalously fast regions. These are interpreted using a recent plate tectonic reconstruction in terms of current and former subduction systems. Several strong anomalies are related to current subduction. The inferred slab lengths and positions are consistent with Neogene subduction beneath the New Britain and Halmahera arcs, and at the Tonga and the New Hebrides trenches where there has been rapid rollback of subduction hinges since about 10 Ma. There are several deeper flat-lying anomalies which are not related to present subduction and we interpret them as former subduction zones overridden by Australia since 25 Ma. Beneath the Bird’s Head and Arafura Sea is an anomaly interpreted to be due to north-dipping subduction beneath the Philippines-Halmahera arc between 45 and 25 Ma. A very large anomaly extending from the Papuan peninsula to the New Hebrides, and from the Solomon Islands to the east Australian margin, is interpreted to be the remnant of south-dipping subduction beneath the Melanesian arc between 45 and 25 Ma. This interpretation implies that a flat-lying slab can survive for many tens of millions of years at the bottom of the upper mantle. In the lower mantle there is a huge anomaly beneath the Gulf of Carpentaria and east Papua New Guinea. This is located above the position where the tectonic model interprets a change in polarity of subduction from north-dipping to south-dipping between 45 and 25 Ma. We suggest this deep anomaly may be a slab subducted beneath eastern Australian during the Cretaceous, or subducted north of Australia during the Cenozoic before 45 Ma. The tomography also supports the tectonic interpretation which suggests little Neogene subduction beneath western New Guinea since no slab is imaged south of the New Guinea trench. However, one subduction zone in the tectonic model and many others, that associated with the Trobriand trough east of Papua New Guinea and the Miocene Maramuni arc, is not seen in the tomographic images and may require reconsideration of currently accepted tectonic interpretations.     

Modeling of Wide-Angle Seismic Attributes Using the Gaussian Beam Method

In this study, observed seismic attributes from shot gather 11 of the SAREX experiment are used to derive a preliminary velocity and attenuation model for the northern end of the profile in southern Alberta. Shot gather 11 was selected because of its prominent Pn arrivals and good signal to noise ratio. The 2-D Gaussian beam method was used to perform the modeling of the seismic attributes including travel times, peak envelope amplitudes and pulse instantaneous frequencies for selected phases. The preliminary model was obtained from the seismic attributes from shot gather 11 starting from prior tomographic results. The amplitudes and instantaneous frequencies were used to constrain the velocity and attenuation structure, with the amplitudes being more sensitive to the velocity gradients and the instantaneous frequencies more sensitive to the attenuation structure. The resulting velocity model has a velocity discontinuity between the upper and lower crust, and lower velocity gradients in the upper and lower crust compared to earlier studies. The attenuation model has Q _p ^-1 values between 0.011 and 0.004 in the upper crust, 0.0019 in the lower crust and a laterally variable Q _p ^-1 in the upper mantle. The Q _p ^-1 values are similar to those found in Archean terranes from other studies. Although the results from a single gather are non-unique, the initial model derived here provides a self-consistent starting point for a more complete seismic attribute inversion for the velocity and attenuation structure.