Changing patterns of Pennsylvanian coal-swamp vegetation and implications of climatic control on coal occurrence

Improved regional and interregional stratigraphic correlations of Pennsylvanian strata permit comparisons of vegetational changes in Euramerican coal swamps. The coal-swamp vegetation is known directly from in situ coal-ball peat deposits from more than 65 coals in the United States and Europe. Interpretations of coal-swamp floras on the basis of coal-ball peat studies are extended to broader regional and stratigraphic patterns by use of coal palynology. Objectives of the quantitative analyses of the vegetation in relation to coal are to determine the botanical constituents at the peat stage and their environmental implications for plant growth and peat accumulation. Morphological and paleoecological analyses provide a basis for deducing freshwater regimes of coal swamps.Changes in composition of Pennsylvanian coal-swamp vegetation are quire similar from one paralic coal region to another and show synchrony that is attributable to climate. Paleobotany and paleogeography of the Euramerican province indicate a moist tropical paleoclimate. Rainfall, runoff and evapotranspiration were the variable climatic controls in the distribution of coal-swamp vegetation, peat accumulation and coal resources. In relative terms of climatic wetness the Pennsylvanian Period is divisible into five intervals, which include two relatively drier intervals that developed during the Lower-Middle and Middle-Upper Pennsylvanian transitions. The climate during Early Pennsylvanian time was moderately wet and the median in moisture availability. Early Middle Pennsylvanian was drier, probably seasonally dry-wet; late Middle Pennsylvanian was the wettest in the Midcontinent; early Late Pennsylvanian was the driest; and late Late Pennsylvanian was probably the wettest in the Dunkard Basin. The five climatic intervals represent a general means of dividing coal resources within each region into groups with similar botanical constituents and environments of peat accumulation. Regional differences in basinal geology and climate were significant variables, but the synchronous control of paleoclimate was of primary importance.     

Towards the detection and attribution of an anthropogenic effect on climate

It has been hypothesized recently that regional-scale cooling caused by anthropogenic sulfate aerosols may be partially obscuring a warming signal associated with changes in greenhouse gas concentrations. Here we use results from model experiments in which sulfate and carbon dioxide have been varied individually and in combination in order to test this hypothesis. We use centered [R (t)] and uncentered [C (t)] pattern similarity statistics to compare observed time-evolving surface temperature change patterns with the model-predicted equilibrium signal patterns. We show that in most cases, the C (t) statistic reduces to a measure of observed global-mean temperature changes, and is of limited use in attributing observed climate changes to a specific causal mechanism. We therefore focus on R (t), which is a more useful statistic for discriminating between forcing mechanisms with different pattern signatures but similar rates of global mean change. Our results indicate that over the last 50 years, the summer (JJA) and fall (SON) observed patterns of near-surface temperature change show increasing similarity to the model-simulated response to combined sulfate aerosol/CO₂ forcing. At least some of this increasing spatial congruence occurs in areas where the real world has cooled. To assess the significance of the most recent trends in R (t) and C (t), we use data from multi-century control integrations performed with two different coupled atmosphere-ocean models, which provide information on the statistical behavior of 'unforced' trends in the pattern correlation statistics. For the combined sulfate aerosol/CO₂ experiment, the 50-year R (t) trends for the JJA and SON signals are highly significant. Results are robust in that they do not depend on the choice of control run used to estimate natural variability noise properties. The R (t) trends for the CO₂-only signal are not significant in any season. C (t) trends for signals from both the CO₂-only and combined forcing experiments are highly significant in all seasons and for all trend lengths (except for trends over the last 10 years), indicating large global-mean changes relative to the two natural variability estimates used here. The caveats regarding the signals and natural variability noise which form the basis of this study are numerous. Nevertheless, we have provided first evidence that both the largest-scale (global-mean) and smaller-scale (spatial anomalies about the global mean) components of a combined CO₂/anthropogenic sulfate aerosol signal are identifiable in the observed near-surface air temperature data. If the coupled-model noise estimates used here are realistic, we can be highly confident that the anthropogenic signal that we have identified is distinctly different from internally generated natural variability noise. The fact that we have been able to detect the detailed spatial signature in response to combined CO₂ and sulfate aerosol forcing, but not in response to CO₂ forcing alone, suggests that some of the regional-scale background noise (against which we were trying to detect a CO₂-only signal) is in fact part of the signal of a sulfate aerosol effect on climate. The large effect of sulfate aerosols found in this study demonstrates the importance of their inclusion in experiments designed to simulate past and future climate change. Received: 10 November 1994 / Accepted: 19 July 1995     

The Application of Petroleum Hydrocarbon Fingerprint Characterization in Site Investigation and Remediation

Tremendous resources have been and continue to be spent investigating and remediating petroleum hydrocarbon compounds (PHCs) in soil and ground water. Investigating and planning a remedial strategy for sites affected by PHCs is often a challenging task because of the complex chemical nature of the PHCs. the complex regulatory environment related to PHC cleanup, and the use of analytical methods that provide quantitation but not identification of PHCs. From a technical standpoint, the PHC impacting soil and/or ground water is frequently inadequately characterised, both in identification as well as in is general properties (solubility, toxicity). From a regulatory standpoint, promulgated or recommended total petroleum hydrocarbon (TPH) cleanup levels generally relate to assumed properties of specific unweathered products and are inconsistent among different agencies and regions. This produces a prime situation for unwillingly spending more resources on investigation or remediation than may be necessary, especially when the PHC in the subsurface has different properties from unweathered products such as gasoline or diesel.
Accurately identifying the PHC and its nature, a process known as fingerprint characterization, is critical to the determination of appropriate regulatory goals and design of cost-effective remedial approaches. This paper presents several case studies in which fingerprint characterization made a significant difference in the project outcome. In each instance the nature of the organic material was better understood, the regulatory cleanup levels were negotiated based on the nature of the material, and a remedial approach was implemented that differed significantly from and was generally less costly than what would have been required without fingerprint characterization data.     

Carbonate equilibria in hydrothermal systems: First ionization of carbonic acid in NaCl media to 300°C

The ionization quotients of aqueous carbon dioxide (carbonic acid) have been precisely determined in NaCl media to 5 m and from 50° to 300°C using potentiometric apparatus previously developed at Oak Ridge National Laboratory. The pressure coefficient was also determined to 250°C in the same media. These results have been combined with selected information in the literature and modeled in two ways to arrive at the best fits and to derive the thermodynamic parameters for the ionization reaction, including the equilibrium constant, activity coefficient quotients, and pressure coefficients. The variation with temperature of the two fundamental quantities $\text{Δ}\text{V}\text{?}{}^{\mathrm{o}}$ and $\text{Δ}\text{C}\text{?}{}^{\mathrm{o}}{}_{\mathrm{p}}$ were examined along the saturation vapor pressure curve and at constant density. The results demonstrated again that for reactions with minimal electrostriction changes the magnitudes and variations of $\text{Δ}\text{C}\text{?}{}^{\mathrm{o}}{}_{\mathrm{p}}$ and $\text{Δ}\text{V}\text{?}{}^{\mathrm{o}}$ with temperature are small and, in addition, $\text{Δ}\text{C}\text{?}{}_{\mathrm{p}}$ and $\text{Δ}\text{V}\text{?}$ are approximately independent of salt concentration.The results have also been applied to an examination of the solubility of calcite as a function of pH (in a given NaCl medium) for the neutral to acidic region both for systems with fixed CO₂ pressure and systems where the calcium ion concentration equals the concentration of carbon. The pH of saturated solutions of calcite with P_CO2 of 12 bars increases from 5.1 to 5.5 between 100° and 300°C.     

Dissolution of secondary copper sulphides using complex-forming agents (EDTA,EDA). Part I: Covellite dissolution in EDTA and EDA

Problems of dissolution of the so-called secondary copper sulphides are very important for dynamic as well as percolation leaching of ores. This paper deals with dissolution kinetics of sulphides in an alkaline medium, using complex-forming agents in connection with possibility to leach basic, partially oxidized ores. Natural minerals and their polydispersions were investigated and the so-called geometrical model was used for evaluation. Basic dependences of the dissolution rate on the reagent concentration and pH value of the leaching solution were found and an attempt at their mathematical expression and physical interpretation was made. The first part of this work refers to the systems of covellite-ethylene diamine tetra-acetic acid (EDTA) and covellite-ethylene diamine (EDA). The established dependences are not only of theoretical but also of practical importance.     

Dissolution of secondary copper sulphides using complex-forming agents (EDTA,EDA). Part II: Chalcocite dissolution in EDTA and EDA

This work is immediate continuation of Part I, using an identical method and evaluation for kinetic studies. The systems chalcocite-ethylene diamine tetra-acetic acid and chalcocite-ethylene diamine were studied. It was necessary to refine the geometrical model method for chalcocite in order to establish dissolution kinetics of polydispersions. This work confirms that chalcocite leaching proceeds through covellite even in the medium of complex-forming agents and kinetic equations for both leaching stages were evaluated with an attempt at physical interpretation.     

Vertical concentration profiles of lead in the Central Pacific at 15°N and 20°S

Concentrations of lead were measured in a surface transect and at two vertical profile stations (15°N and 20°S) in the Central Pacific. These measurements complement similar measurements made earlier in the North Pacific at 33°N and in the Northwest Atlantic at 34°N [1,2], as well as recent measurements of eolian lead input fluxes near each of these locations [3]. The new transect of surface water concentrations of lead corroborates previous measurements, which decrease from 13 ng/kg at 30°N to 4 ng/kg at 17°S in the Central Pacific [4]. This transect gradient is shown to overlie a similar geographic gradient of subsurface maximum concentrations of lead in the three Pacific vertical profile stations, decreasing from 14 ng/kg at 33°N to 11 ng/kg at 14°N to 2.5 ng/kg at 20°S. Lead concentrations at each of those locations exhibit maxima at 400 m, decreasing concentrations to 2500 m and approximately concentrations of 0.8–1.1 ng/kg below that depth. The subsurface maximum at the northwest Atlantic profile station (36 ng/kg at 34°N) is also congruent with surface water lead concentrations which decrease from 806 ng/kg to 32 ng/kg in an offshore transect from Rhode Island to 34°N, 66°W [5], and the shape of the Atlantic profile is congruent with those in the Pacific. There is a positive correlation between the magnitudes of eolian lead input fluxes and the magnitudes of the upper water maxima in lead concentration profiles at corresponding locations as follows: South Pacific easterlies 3 ng/cm² yr vs. 2.5 ng/kg; North Pacific easterlies 6 ng/cm² yr vs. 11 ng/kg; North Pacific westerlies 50 ng/cm² yr vs. 14 ng/kg; and North Atlantic westerlies 170 ng/cm² yr vs. 36 ng/kg.This relationship enables one to view the anthropogenic perturbations of the marine lead cycle on a global scale, since the industrial origin of eolian and seawater lead has been established by correlations between geographic patterns of industrial lead emissions to the atmosphere and isotopic ratios of industrial leads [3] and by geographic patterns of Pb/silicate-dust ratios and lead isotopic ratios in ocean surface waters [3–5]. These new data coupled with earlier biogeochemical data indicate that surface water concentrations of lead in the North Pacific and North Atlantic are now conservatively estimated to be 8 to 20-fold greater and those in the South Pacific are 2-fold greater than natural concentrations because of industrial emissions of lead to the atmosphere.     

Seasonal variation in stable oxygen and carbon isotope values recovered from modern lacustrine freshwater mollusks: paleoclimatological implications for sub-weekly temperature records

A fingernail clam (Sphaerium simile, Sphaeriidae) from Science Lake, a small watershed located in Allegany State Park, New York, USA and a zebra mussel (Dreissena polymorpha, Dreissenidae) from Keuka Lake, New York, the third largest Finger Lake of central New York, were selected to evaluate the applicability of using ¹⁸O_(CaCO3) and ¹³O_(CaCO3) values for sub-weekly climate records. Seasonal variation in ¹⁸O_(CaCO3) values was compared with predicted equilibrium values to test the hypothesis that lacustrine molluscs produce shell aragonite according to environmental variables. For the purpose of comparison, aragonite temperature-fractionation equations determined by Grossman& Ku (1986) and Patterson et al. (1993) were used. Sphaerium simile appears to produce ¹⁸O_(CaCO3) values predicted by Patterson et al. (1993), while Dreissena polymorpha produces ¹⁸O_(CaCO3) values in agreement with Grossman & Ku (1986). We attribute the difference to family-specific temperature-fractionation relationships. Because both types of mollusc record climate variables with a high degree of integrity, they should each serve as excellent paleoclimate proxies.The fingernail clam collected from a small watershed exhibits higher variation about the seasonal pattern than did the zebra mussel collected from a large watershed. This is attributed to the increased sensitivity of the small watershed to storm perturbation. Analysis of fossil molluscs from such watersheds might be useful in discerning paleo-storminess.