Formic and acetic acids in atmospheric condensate in Wilmington,North Carolina

Formic and acetic acids occurred in atmospheric condensate with concentrations similar to rainwater collected in Wilmington, North Carolina, during the sampling period from June to October of 1990. Atmospheric concentrations of these acids (calculated from the condensate concentrations) were higher in continental versus maritime air masses. Concentrations of formic and acetic acids were correlated with each other in both condensate and air. Traffic was a source of acetic acid and of bisulfite to atmospheric condensate in this study.     

Thermodynamic stability of CoOOH and its coprecipitation with manganese

A precipitate of cobalt oxyhydroxides formed by bubbling oxygen through a dilute solution of Co(NO₃)₂ held at pH 9.0 and 25°C was aged for 23 months in contact with the original solution, with access to atmospheric oxygen. Co₃O₄ and CoOOH were identified in the precipitate by X-ray diffraction. Chemical equilibria involving these solids were evaluated by measurements of solution pH and Co²⁺ activities and by redox potential measurements and gave a $\text{ΔG}{}_{\mathrm{coOOH}}{}^0$ of $\text{?92.3 ± 0.5 kcal/mole}$. This value and other thermodynamic data show relative feasibility of hypothetical reaction steps and changes in reaction paths during automated coprecipitation titrations and subsequent aging of a precipitate that finally contained βMnOOH, MnO₂ (birnessite) and CoOOH.     

Nonequilibrium models for predicting forms of precipitated manganese oxides

Manganese oxides precipitated by bubbling air through 0.01 molar solutions of MnCl₂, Mn(NO₃)₂, MnSO₄, or Mn(ClO₄)₂ at a constantly maintained pH of 8.5 to 9.5 at temperatures of 25°C or higher consisted mainly of hausmannite, Mn₃O₄. At temperatures near 0°C, but with other conditions the same, the product is feitknechtite, βMnOOH, except that if the initial solution is MnSO₄ and the temperature is near 0°C the product is a mixture of manganite, γMnOOH and groutite, αMnOOH.All these oxides are metastable in aerated solution and alter by irreversible processes to more highly oxidized species during aging. A two-step nonequilibrium thermodynamic model predicts that the least stable species, βMnOOH, should be most readily converted to MnO₂. Some preparations of βMnOOH aged in their native solution at 5°C attained a manganese oxidation state of +3.3 or more after 7 months. Hausmannite aged at 25°C altered to γMnOOH. The latter is more stable than a or βMnOOH, and manganese oxidation states above 3.0 were not reached in hausmannite precipitates during 4 months of aging. Initial precipitation of MnCO₃ rather than a form of oxide is likely only where oxygen availability is very low.Composition of solutions and oxidation state and morphology of solids were determined during the aging process by chemical analyses, X-ray and electron diffraction and transmission electron micrographs.     

Quantifying geographic variations in associations between alcohol distribution and violence: a comparison of geographically weighted regression and spatially varying coefficient models

Past studies consistently indicate measurable local associations between alcohol distribution and the incidence of violence. These results, coupled with measurements of spatial correlation, reveal the importance of spatial analysis in the study of the interaction of alcohol and violence. While studies increasingly incorporate spatial correlation among model residuals to improve precision and reduce bias, to date, most analyses assume associations that are constant and independent of location, an assumption coming under increasing scrutiny in the quantitative geography literature. In this paper, we review and contrast two approaches for the estimation of and inference for spatially heterogeneous effects (i.e., associative factors whose impacts on the outcome of interest vary throughout geographic space). Specifically, we provide an in-depth comparison of “geographically weighted regression” models (allowing covariate effects to vary in space but only allowing relatively ad hoc inference) with “variable coefficient” models (allowing varying effects via spatial random fields and providing model-based estimation and inference, but requiring more advanced computational techniques). We compare the approaches with respect to underlying conceptual structures, computational implementation, and inferential output. We apply both approaches to violent crime, illegal drug arrest, and alcohol distribution data from Houston, Texas and compare results in light of the differing methodological structures of the two approaches.     

Garnet growth in a metapelite from the Moinian rocks of Northern Sutherland,Scotland

Compositional profiles of a series of garnets, extracted from a pelitic schist occurring in the Moinian rocks of Northern Sutherland, have been established. The profiles are complex and do not conform to a simple fractionation model. A model to explain them is suggested.     

Assessment of δ13C and C/N ratios in bulk organic matter as palaeosalinity indicators in Holocene and Lateglacial isolation basin sediments,northwest Scotland

Carbon isotopes (δ¹³C) and C/N ratios from bulk organic matter have recently been used as alternative proxies for relative sea‐level (RSL) reconstruction where there are problems associated with conventional biological indictors. A previous study on a single isolation basin (Upper Loch nan Eala) in northwest Scotland has shown a clear relationship between δ¹³C, C/N ratios and palaeosalinity from Younger Dryas and Holocene aged sediments. In this paper we present results of δ¹³C and C/N ratio analyses from other isolation basins in northwest Scotland over the Holocene and the Lateglacial period in order to validate this technique. The results from the Holocene sequences support the earlier findings that this technique can be used to identify RSL change from isolation basins over the Holocene in this region. The relationship between δ¹³C, C/N ratios and RSL change is not apparent in sediments of Lateglacial age. Other environmental variables such as atmospheric CO₂ concentration, poor vegetation development and temperature influence δ¹³C values during this period. Copyright © 2007 John Wiley & Sons, Ltd.     

Coupled HM analysis using zero‐thickness interface elements with double nodes—Part II: Verification and application

In a companion Part I of this paper (Int. J. Numer. Anal. Meth. Geomech. 2008; DOI: 10.1002/nag.735 ), a coupled hydro‐mechanical (HM) formulation for geomaterials with discontinuities based on the finite element method (FEM) with double‐node, zero‐thickness interface elements was developed and presented. This Part II paper includes the numerical solution of basic practical problems using both the staggered and the fully coupled approaches. A first group of simulations, based on the classical consolidation problem with an added vertical discontinuity, is used to compare both the approaches in terms of accuracy and convergence. The monolithic or fully coupled scheme is also used in an application example studying the influence of a horizontal joint in the performance of a reservoir subject to fluid extraction. Results include a comparison with other numerical solutions from the literature and a sensitivity analysis of the mechanical parameters of the discontinuity. Some simulations are also run using both a full non‐symmetric and a simplified symmetric Jacobian matrix. On top of verifying the model developed and its capability to reflect the conductivity changes of the interface with aperture changes, the results presented also lead to interesting observations of the numerical performance of the methods implemented. Copyright © 2008 John Wiley & Sons, Ltd.     

Detecting infiltration and impacts of introduced water using strontium isotopes

Water introduced to surface drainages, such as agricultural and roadway runoff, mine drainage, or coalbed natural gas (CBNG)-produced water, potentially can be of environmental concern. In order to mitigate potential environmental effects, it may be important to be able to trace water discharged to the surface as it infiltrates and interacts with near-surface aquifers. We have chosen to study water withdrawn during CBNG production for isotope tracing in the hyporheic zone because it poses a variety of economic, environmental, and policy issues in the Rocky Mountain states. Ground water quality must be protected as CBNG water is added to semiarid ecosystems. Strontium (Sr) isotopes are effective fingerprints of the aquifer from which water originates. In this study, CBNG water was found to have a higher (87)Sr/(86)Sr ratio than the local alluvial aquifer water. This measurable difference allows the strontium isotope ratio and concentration to be used as tracers of CBNG water following its discharge to the surface. The dissolution and mobilization of salts from soil are an important contributor to ground water quality degradation. In the Powder River basin of Wyoming, the soils are calcium carbonate-buffered systems. The chemical similarity of strontium to calcium allows it to substitute into calcium minerals and enabled us to use strontium isotopes to identify calcium salts mobilized from the soil. Strontium isotopes are an effective monitor of the source of ions and the volume and direction of introduced water flow in the hyporheic zone.     

Temperature induced decoupling of enzymatic hydrolysis and carbon remineralization in long-term incubations of Arctic and temperate sediments

Extracellular enzymatic hydrolysis of high-molecular weight organic matter is the initial step in sedimentary organic carbon degradation and is often regarded as the rate-limiting step. Temperature effects on enzyme activities may therefore exert an indirect control on carbon mineralization. We explored the temperature sensitivity of enzymatic hydrolysis and its connection to subsequent steps in anoxic organic carbon degradation in long-term incubations of sediments from the Arctic and the North Sea. These sediments were incubated under anaerobic conditions for 24 months at temperatures of 0, 10, and 20 °C. The short-term temperature response of the active microbial community was tested in temperature gradient block incubations. The temperature optimum of extracellular enzymatic hydrolysis, as measured with a polysaccharide (chondroitin sulfate), differed between Arctic and temperate habitats by about 8-13 °C in fresh sediments and in sediments incubated for 24 months. In both Arctic and temperate sediments, the temperature response of chondroitin sulfate hydrolysis was initially similar to that of sulfate reduction. After 24 months, however, hydrolysis outpaced sulfate reduction rates, as demonstrated by increased concentrations of dissolved organic carbon (DOC) and total dissolved carbohydrates. This effect was stronger at higher incubation temperatures, particularly in the Arctic sediments. In all experiments, concentrations of volatile fatty acids (VFA) were low, indicating tight coupling between VFA production and consumption. Together, these data indicate that long-term incubation at elevated temperatures led to increased decoupling of hydrolytic DOC production relative to fermentation. Temperature increases in marine sedimentary environments may thus significantly affect the downstream carbon mineralization and lead to the increased formation of refractory DOC.