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.     

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.     

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.     

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.     

Chemical denudation rates in Kärkevagge, Swedish Lapland

This study examines the spatial and temporal variability of chemical denudation rates in Kärkevagge, northern Sweden. The chemical flux rates within the valley are strongly influenced by the local geology. Chemical denudation rates determined for the study period are more than double those previously reported in the literature for this valley. Rates of greater than 46t km⁻² a⁻¹ were measured at the valley mouth over the course of the melt season. This difference is likely due to differences in measurement technique compared to that used by past researchers. This rate is also much higher than for other arctic and alpine watersheds. Chemical denudation in Kärkevagge is comparable to larger temperate rivers. The rapid chemical denudation in Kärkevagge is likely due to sulfide weathering creating acid solutions.     

Chasing a 'loose and baggy monster': almshouses and the geography of charity

This paper goes some way towards redressing the lack of geographical literature on charity through exploring the geography of the British domestic charitable sector. The size and geography of the third sector is outlined, followed by an analysis of how almshouses can be understood as inherently geographical and deeply embedded in local social networks of inclusion as well as exclusion.     

Employment and Socio-spatial Relations in Australia's Cultural Economy

This paper examines the significance and contribution of Australian 'creative' industry activities in light of recent debates on the emergence of the 'cultural economy of cities'. First, census employment data and business location counts are used to illustrate patterns of metropolitan primacy and concentration in the cultural industries both across states and in Sydney. Second, the specificities of the locations of cultural production, and the links between cultural industry activities and wider urban-regional change are explored in more detail. A set of observations of urban-regional change is used to demonstrate how the notion of 'cultural economy' should include complex interactions between the material activities of consumers and producers, and the discursive worlds of image makers and place marketers. Urban renewal, housing market pressures and intra-regional migration all mediate Australian experiences of the 'cultural economy'. Such interactions, in addition to key quantitative data on employment and business activity, suggest important policy considerations.