Comparative DFT study of inner-sphere As(III) complexes on hydrated α-Fe2O3(0001) surface models

The long-recognized risk to human health arising from arsenic-contaminated waters is known to be linked to partitioning reactions between arsenic and natural solid phases. Currently, the ability to predict As surface complexation is limited by the lack of molecular-level understanding of As-solid interactions. In the present study, we use density functional theory (DFT) to model mono-, bi-, and tri-dentate As(III) surface complexes on different (previously proposed) structural models for hydrated hematite, modeled as α-Fe(2)O(3)(0001)-water interfaces. One of the modeled hematite-water interfaces is terminated entirely by hydroxyl surface functional groups, comprised of hematite lattice oxygen atoms. The other hematite-water interface is an iron-terminated model in which the outermost oxygen functional groups are water (and water dissociation product) ligands. We report the DFT trends in adsorption energies in terms of As-hematite coordination, hematite surface geometry/stoichiometry, and oxygen functional group identity. The DFT energetics predict that a monodentate As(III) surface complex is preferred on both hematite-water structures, suggesting that the two structural models here employed do not sufficiently represent the true surface structure to reproduce the experimental observation of As(III) bidentate coordination. However, the results do elucidate fundamental concepts of interface reactivity: A key result, supported by electronic structure analysis, is that ligand oxygen functional groups cannot be treated on equal ground with true surface oxygen functional groups. For the systems modeled here the distinction between surface and ligand functional groups supersedes the differences in oxygen coordination with surface Fe. We discuss the impact of this finding on the application of bond-valence-based predictions of mineral-water reactivity, and use the results of this study to pose questions and directions for ongoing modeling efforts aimed at linking macroscopic reactivity with molecular-level understanding.     

Availability,addiction and alternatives: three criteria for assessing the impact of peak minerals on society

The concept of ‘peaks’ in the production of natural resources has attracted attention in the area of energy production, with concerns about ‘peak oil’ driving recent research and investment in alternative sources of energy. There are fundamental and important differences between a peak in the production of oil and peaks in the production of metalliferous minerals, but in both cases production changes from ‘easier and less expensive’ early in a resource’s life to ‘difficult and expensive’ as time progresses. The impacts of this change in production circumstances require critical consideration in the governance of national and sub-national mineral endowments.This paper develops a framework for evaluating the impacts of changing patterns of mineral production. The framework considers three criteria: availability of a resource (considering its geological characteristics and geographical distribution); society’s addiction to the resource (its centrality and criticality to economic, social and environmental systems); and the possibility of finding alternatives (whether the resource can be substituted or recovered). An initial assessment against these criteria provides an overview of how a production peak might affect the production of minerals in Australia and the impacts that this might have on the Australian economy.Assessing important resources against these three criteria will be imperative in future considerations regarding the roles minerals and metals play as service providers in our economic, social and environmental systems. Additionally, this analysis should prompt a reassessment of the value of minerals beyond economic measures. Indicators derived from these criteria will inform strategies that can address future changes in production characteristics – meeting challenges with strong governance, and realising opportunities with proactive policy.     

Assessment of coastal storm impacts on contaminant body burdens of oysters collected from the gulf of Mexico

This study evaluated changes in oyster tissue contaminant levels following North Atlantic tropical cyclones to determine if changes in contaminant concentrations were predictable. The basis for this study was analysis of coastal chemical contaminant data from the National Oceanic and Atmospheric Administration's (NOAA) National Status and Trends Mussel Watch Program and NOAA's National Weather Service storm track data. The tendency for contaminant (metals and organic compounds) body burdens to increase or decrease in oyster tissue after a storm was assessed using contingency and correspondence analyses. Post-storm contaminant levels in oysters revealed a consistent pattern of distribution, which could be described as follows: (1) most of the organic contaminants stay within their long-term concentration ranges, (2) very few organic contaminants decreased, and (3) metals overwhelmingly tend to increase.     

A study of the corrosion products of mild steel in high ionic strength brines

The corrosion layer on steel surfaces that formed after exposure to waste isolation pilot plant (WIPP) brines under anoxic conditions was characterized for chemical composition, thickness and phase composition. The chemical composition of the corrosion layer was determined both by X-ray photoelectron spectroscopy (XPS) and by chemical analysis of acid solutions used to remove the corrosion layer. Atomic force microscopic (AFM) images indicated that the brine-corroded surface layer shows extensive granulation along the contours of the steel surface that is characteristic of sharp polishing marks. The corrosion layer seemed to be porous and could be dissolved and detached in dilute hydrochloric acid. The corrosion layer appears to be composed of iron oxides with some ionic substitutions from the brines. The 77 K M?ssbauer spectrum recorded for iron powder leached under similar conditions indicated the corrosion layer was comprised principally of green rust.     

Seasonal anorexia in the male red-sided garter snake,<Emphasis Type="Italic"> Thamnophis sirtalis parietalis</Emphasis>

Many animals show seasonal shifts in behaviors that coincide with breeding, migration, or hibernation. These behavioral shifts provide ideal opportunities to study the regulation of behavior. The red-sided garter snake (Thamnophis sirtalis parietalis) spends 8 months of the year inactive in underground hibernacula, 1 month breeding, and 3 months feeding to build up enough energy stores to survive the following winter. Although they emerge from 8 months of hibernation with severely depleted energy reserves, they do not feed until weeks later, after the breeding season. We tested the hypothesis that this lack of feeding during the breeding season is due to a shift in behavior rather than the distribution of food and potential mates. Male garter snakes were given a series of choices between pursuing a breeding or feeding opportunity. The proportion of tests in which males selected feeding over breeding gradually increased throughout the study period, reaching almost 100% in the final tests. Males also were given opportunities to feed and court at the beginning and end of the study. Males initially refused food and courted females, but when retested at the end of the study they fed and did not court females. Thus aphagia during the breeding season is due at least in part to an endogenous shift in behavior.Communicated by P. Weatherhead     

Induced triploidy in the soft-shelled clam Mya arenaria: energetic implications

Given that triploid adult bivalves reportedly grow larger and faster than their diploid siblings, such differences should be traceable to variation in energy allocation. In one proposed mechanism, retarded gametogenesis found in triploid adults may allow them more energy for somatic growth. Another hypothesis states that triploids are more heterozygous; increased heterozygosity has been positively correlated with enhanced growth. Juvenile soft-shelled clams, Mya arenaria, were treated with cytochalasin B to induce triploidy and examined with respect to components of a balanced energy equation (C=P+R+E). The variables measured were oxygen uptake (V _{o 2}), filtration rate (FR), dry tissue weight, shell length, shell height and shell inflation. Energy budgets were constructed and diploid and triploid groups compared. Few significant differences were found between diploid and triploid juvenile clams with respect to energy budget components. However, at seven loci assayed electrophoretically the triploid individuals were nearly twice as heterozygous as their diploid siblings. Moreover, tripoloid variances were less than diploid variances for every variable measured. Increased heterozygosity has been correlated with the decreased variance of morphological parameters. This study is believed to be the first to show decreased variance of physiological properties as well as morphological characters. Overall the data clearly indicate that energy allocation in juvenile M. arenaria is not related to ploidy.     

Reducing sediment and phosphorus in tributary waters with alum and polyacrylamide

The Salton Sea is the largest inland water body in California, covering an area of 980 km(2). Inflow to the Salton Sea (1.6 km(3) yr(-1)) is predominately nutrient-rich agricultural wastewater, which has led to eutrophication. Because internal phosphorus release from the bottom sediments is comparatively low and external phosphorus loading to the Salton Sea is high, reduction of tributary phosphorus is expected to reduce algal blooms, increase dissolved oxygen, and reduce odors. Removing both dissolved phosphorus and phosphorus-laden sediment from agricultural drainage water (ADW) should decrease eutrophication. Both alum and polyacrylamide (PAM) are commonly used in wastewater treatment to remove phosphorus and sediment and were tested for use in tributary waters. Laboratory jar tests determined PAM effectiveness (2 mg L(-1)) for turbidity reduction as cationic > anionic = nonionic. Although cationic PAM was the most effective at reducing turbidity at higher speeds, there was no observed difference between the neutral and anionic PAMs at velocity gradients of 18 to 45 s(-1). Alum (4 mg L(-1) Al) reduced turbidity in low energy systems (velocity gradients < 10 s(-1)) by 95% and was necessary to reduce soluble phosphorus, which comprises 47 to 100% of the total P concentration in the tributaries. When PAM was added with alum, the anionic PAM became ineffective in aiding flocculation. The nonionic PAM (2 mg L(-1)) + alum (4 mg L(-1) Al) is recommended to reduce suspended solids in higher energy systems and reduce soluble P by 93%.     

Effects of interactions between anthropogenic stressors and recurring perturbations on ecosystem resilience and collapse

Insights into declines in ecosystem resilience and their causes and effects can inform preemptive action to avoid ecosystem collapse and loss of biodiversity, ecosystem services, and human well-being. Empirical studies of ecosystem collapse are rare and hampered by ecosystem complexity, nonlinear and lagged responses, and interactions across scales. We investigated how an anthropogenic stressor could diminish ecosystem resilience to a recurring perturbation by altering a critical ecosystem driver. We studied groundwater-dependent, peat-accumulating, fire-prone wetlands known as upland swamps in southeastern Australia. We hypothesized that underground mining (stressor) reduces resilience of these wetlands to landscape fires (perturbation) by diminishing groundwater, a key ecosystem driver. We monitored soil moisture as an indicator of ecosystem resilience during and after underground mining. After landscape fire, we compared responses of multiple state variables representing ecosystem structure, composition, and function in swamps within the mining footprint with unmined reference swamps. Soil moisture declined without recovery in swamps with mine subsidence (i.e., undermined), but was maintained in reference swamps over 8 years (effect size 1.8). Relative to burned reference swamps, burned undermined swamps showed greater loss of peat via substrate combustion; reduced cover, height, and biomass of regenerating vegetation; reduced postfire plant species richness and abundance; altered plant species composition; increased mortality rates of woody plants; reduced postfire seedling recruitment; and extirpation of a hydrophilic animal. Undermined swamps therefore showed strong symptoms of postfire ecosystem collapse, whereas reference swamps regenerated vigorously. We found that an anthropogenic stressor diminished the resilience of an ecosystem to recurring perturbations, predisposing it to collapse. Avoidance of ecosystem collapse hinges on early diagnosis of mechanisms and preventative risk reduction. It may be possible to delay or ameliorate symptoms of collapse or to restore resilience, but the latter appears unlikely in our study system due to fundamental alteration of a critical ecosystem driver. Efectos de las interacciones entre los estresantes antropogénicos y las perturbaciones recurrentes sobre la resiliencia y el colapso de los ecosistemas     

Diversity attitudes and norms: the role of ethnic identity and relational demography

This study investigated attitudes and subjective norms related to workplace diversity initiatives and intentions to engage in diversity‐related behaviors in a sample of 852 public service employees. Participants completed a survey measuring behavioral intentions, attitudes, belief‐based norms, ethnic identity achievement, and demographic characteristics. Comparisons were made between people of color and Whites as well as between those with high and low ethnic identity achievement. Results showed a triple interaction among supervisor race, employee race, and employee ethnic identity achievement. Specifically, among people of color with high ethnic identity achievement, having a supervisor of color was more strongly associated with positive views of subjective norms toward inclusive behavior, understanding others, and treating others with respect than among people of color with low ethnic identity achievement. Implications of these findings and directions for future research are discussed. Copyright © 2006 John Wiley & Sons, Ltd.