Fire Promotes Arsenic Mobilization and Rapid Arsenic(III) Formation in Soil via Thermal Alteration of Arsenic-Bearing Iron Oxides

Arsenic in oxic surface soils readily associates with Fe(III) oxide minerals such as ferrihydrite and goethite, predominantly as As(V). Fires are a common feature in many landscapes, creating high-temperature soil conditions which drive thermal transformation of these As(V)-bearing minerals. However, it is unknown whether fire-induced transformation of ferrihydrite and goethite can alter the mobility of As, or alter As(V) speciation (e.g., via pyrolysis induced electron-transfer generating the more mobile and toxic inorganic As(III) species). Here, we subject an organic-rich soil (∼15% organic C) mixed (4:1) with As(V)-bearing ferrihydrite and goethite (total As of 2.8–3.8 μmol g-1), to various temperatures (200–800°C) and heating durations (5–120 min) and examine the consequences for As and Fe via X-ray absorption spectroscopy, X-ray diffraction, 57Fe Mössbauer spectroscopy and selective extracts. We show that heating transformed both ferrihydrite and goethite to mainly maghemite at temperatures >400°C and tended to increase exchangeable surface-complexed As (AsEx) in ferrihydrite yet decrease AsEx in goethite. We demonstrate for the first time that ferrihydrite and goethite-bound As(V) can be rapidly reduced to As(III) during heating of organic-rich soil. Electrons were readily transferred to both Fe(III) and As(V), with reduction of As(V) to As(III) peaking at intermediate temperatures and time periods (maxima of ∼88% for ferrihydrite; ∼80% for goethite). Although As(III) formation was fast (within 5–10 min at temperatures >400°C), it was followed by partial re-oxidation to As(V) at higher temperatures and longer time intervals. Additionally, combusted As-bearing ferrihydrite and goethite soil-mixtures display greatly enhanced (2–3 orders of magnitude) mobilization of inorganic As(III)aq species upon re-wetting with water. Mobilization of As(III)aq was positively correlated with solid-phase As(III) formation and was greater for goethite than ferrihydrite. These findings challenge the current prevailing view that As(V) reduction to As(III) in soil is mainly limited to waterlogged conditions and suggest that moderate-temperature fires of short duration in oxic soils, may generate substantial labile As(III) species and lead to a pulse of As(III)aq mobilization upon initial rainfall and re-wetting. Further investigation is recommended to explore the consequences for arsenic cycling in fire-prone natural landscapes and agricultural systems which involve controlled-burn practices

Triple oxygen isotope insight into terrestrial pyrite oxidation.

The mass-independent minor oxygen isotope compositions (Δ'17O) of atmospheric O2 and [Formula: see text] are primarily regulated by their relative partial pressures, [Formula: see text]/[Formula: see text] Pyrite oxidation during chemical weathering on land consumes [Formula: see text] and generates sulfate that is carried to the ocean by rivers. The Δ'17O values of marine sulfate deposits have thus been proposed to quantitatively track ancient atmospheric conditions. This proxy assumes direct [Formula: see text] incorporation into terrestrial pyrite oxidation-derived sulfate, but a mechanistic understanding of pyrite oxidation-including oxygen sources-in weathering environments remains elusive. To address this issue, we present sulfate source estimates and Δ'17O measurements from modern rivers transecting the Annapurna Himalaya, Nepal. Sulfate in high-elevation headwaters is quantitatively sourced by pyrite oxidation, but resulting Δ'17O values imply no direct tropospheric [Formula: see text] incorporation. Rather, our results necessitate incorporation of oxygen atoms from alternative, 17O-enriched sources such as reactive oxygen species. Sulfate Δ'17O decreases significantly when moving into warm, low-elevation tributaries draining the same bedrock lithology. We interpret this to reflect overprinting of the pyrite oxidation-derived Δ'17O anomaly by microbial sulfate reduction and reoxidation, consistent with previously described major sulfur and oxygen isotope relationships. The geologic application of sulfate Δ'17O as a proxy for past [Formula: see text]/[Formula: see text] should consider both 1) alternative oxygen sources during pyrite oxidation and 2) secondary overprinting by microbial recycling

Long-lived space observatories for astronomy and astrophysics

NASA's plan to build and launch a fleet of long-lived space observatories that include the Hubble Space Telescope (HST), the Gamma Ray Observatory (GRO), the Advanced X Ray Astrophysics Observatory (AXAF), and the Space Infrared Telescope Facility (SIRTF) are discussed. These facilities are expected to have a profound impact on the sciences of astronomy and astrophysics. The long-lived observatories will provide new insights about astronomical and astrophysical problems that range from the presence of planets orbiting nearby stars to the large-scale distribution and evolution of matter in the universe. An important concern to NASA and the scientific community is the operation and maintenance cost of the four observatories described above. The HST cost about $1.3 billion (1984 dollars) to build and is estimated to require$160 million (1986 dollars) a year to operate and maintain. If HST is operated for 20 years, the accumulated costs will be considerably more than those required for its construction. Therefore, it is essential to plan carefully for observatory operations and maintenance before a long-lived facility is constructed. The primary goal of this report is to help NASA develop guidelines for the operations and management of these future observatories so as to achieve the best possible scientific results for the resources available. Eight recommendations are given

Probing the structure of the cold dark matter halo with ancient mica

Mica can store (for >1 Gy) etchable tracks caused by atoms recoiling from WIMPs. Ancient mica is a directional detector despite the complex motions it makes with respect to the WIMP "wind". We can exploit the properties of directionality and long integration time to probe for structure in the dark matter halo of our galaxy. We compute a sample of possible signals in mica for a plausible model of halo structure.Comment: 7 pages, 2 figure

Prospective, multisite, international comparison of \u3csup\u3e18\u3c/sup\u3eF-fluoromethylcholine PET/CT, multiparametric MRI, and \u3csup\u3e68\u3c/sup\u3eGa-HBED-CC PSMA-11 PET/CT in men with high-risk features and biochemical failure after radical prostatectomy: Clinical performance and patient outcomes

A significant proportion of men with rising prostate-specific antigen (PSA) levels after radical prostatectomy (RP) fail prostate fossa (PF) salvage radiation treatment (SRT). This study was done to assess the ability of F-fluoromethylcholine ( F-FCH) PET/CT (hereafter referred to as F-FCH), Ga-HBED-CC PSMA-11 PET/CT (hereafter referred to as PSMA), and pelvic multiparametric MRI (hereafter referred to as pelvic MRI) to identify men who will best benefit from SRT. Methods: Prospective, multisite imaging studies were carried out in men who had rising PSA levels after RP, high-risk features, and negative/equivocal conventional imaging results and who were being considered for SRT. F-FCH (91/91), pelvic MRI (88/91), and PSMA (31/91) (Australia) were all performed within 2 wk. Imaging was interpreted by experienced local/central interpreters who were masked with regard to other imaging results, with consensus being reached for discordant interpretations. Expected management was documented before and after imaging, and data about all treatments and PSA levels were collected for 3 y. The treatment response to SRT was defined as a reduction in PSA levels of .50% without androgen deprivation therapy. Results: The median Gleason score, PSA level at imaging, and PSA doubling time were 8, 0.42 (interquartile range, 0.29–0.93) ng/mL, and 5.0 (interquartile range, 3.3–7.6) months. Recurrent prostate cancer was detected in 28% (25/88) by pelvic MRI, 32% (29/91) by F-FCH, and 42% (13/31) by PSMA. This recurrence was found within the PF in 21.5% (19/88), 13% (12/91), and 19% (6/31) and at sites outside the PF (extra-PF) in 8% (7/88), 19% (17/91), and 32% (10/31) by MRI, F-FCH, and PSMA, respectively (P, 0.004). A total of 94% (16/17) of extra-PF sites on F-FCH were within the pelvic MRI field. Intra-pelvic extra-PF disease was detected in 90% (9/10) by PSMA and in 31% (5/16) by MRI. F-FCH changed management in 46% (42/91), and MRI changed management in 24% (21/88). PSMA provided additional management changes over F-FCH in 23% (7/31). The treatment response to SRT was higher in men with negative results or disease confined to the PF than in men with extra-PF disease ( F-FCH 73% [32/44] versus 33% [3/9] [P, 0.02], pelvic MRI 70% [32/46] versus 50% [2/4] [P was not significant], and PSMA 88% [7/ 8] versus 14% [1/7] [P, 0.005]). Men with negative imaging results (MRI, F-FCH, or PSMA) had high (78%) SRT response rates. Conclusion: F-FCH and PSMA had high detection rates for extra-PF disease in men with negative/equivocal conventional imaging results and rising PSA levels after RP. These findings affected management and treatment responses, suggesting an important role for PET in triaging men being considered for curative SRT. 18 18 18 68 18 18 18 18 18 18 18 18 1

The Case for Dynamic Models of Learners' Ontologies in Physics

In a series of well-known papers, Chi and Slotta (Chi, 1992; Chi & Slotta, 1993; Chi, Slotta & de Leeuw, 1994; Slotta, Chi & Joram, 1995; Chi, 2005; Slotta & Chi, 2006) have contended that a reason for students' difficulties in learning physics is that they think about concepts as things rather than as processes, and that there is a significant barrier between these two ontological categories. We contest this view, arguing that expert and novice reasoning often and productively traverses ontological categories. We cite examples from everyday, classroom, and professional contexts to illustrate this. We agree with Chi and Slotta that instruction should attend to learners' ontologies; but we find these ontologies are better understood as dynamic and context-dependent, rather than as static constraints. To promote one ontological description in physics instruction, as suggested by Slotta and Chi, could undermine novices' access to productive cognitive resources they bring to their studies and inhibit their transition to the dynamic ontological flexibility required of experts.Comment: The Journal of the Learning Sciences (In Press

An Assessment of Potential Exposure and Risk from Estrogens in Drinking Water

BACKGROUND. Detection of estrogens in the environment has raised concerns in recent years because of their potential to affect both wildlife and humans. OBJECTIVES. We compared exposures to prescribed and naturally occurring estrogens in drinking water to exposures to naturally occurring background levels of estrogens in the diet of children and adults and to four independently derived acceptable daily intakes (ADIs) to determine whether drinking water intakes are larger or smaller than dietary intake or ADIs. METHODS. We used the Pharmaceutical Assessment and Transport Evaluation (PhATE) model to predict concentrations of estrogens potentially present in drinking water. Predicted drinking water concentrations were combined with default water intake rates to estimate drinking water exposures. Predicted drinking water intakes were compared to dietary intakes and also to ADIs. We present comparisons for individual estrogens as well as combined estrogens. RESULTS. In the analysis we estimated that a child's exposures to individual prescribed estrogens in drinking water are 730-480,000 times lower (depending upon estrogen type) than exposure to background levels of naturally occurring estrogens in milk. A child's exposure to total estrogens in drinking water (prescribed and naturally occurring) is about 150 times lower than exposure from milk. Adult margins of exposure (MOEs) based on total dietary exposure are about 2 times smaller than those for children. Margins of safety (MOSs) for an adult's exposure to total prescribed estrogens in drinking water vary from about 135 to > 17,000, depending on ADI. MOSs for exposure to total estrogens in drinking water are about 2 times lower than MOSs for prescribed estrogens. Depending on the ADI that is used, MOSs for young children range from 28 to 5,120 for total estrogens (including both prescribed and naturally occurring sources) in drinking water. CONCLUSIONS. The consistently large MOEs and MOSs strongly suggest that prescribed and total estrogens that may potentially be present in drinking water in the United States are not causing adverse effects in U.S. residents, including sensitive subpopulations.Johnson & Johnson Pharmaceutical Research and Development, LLC; Pfizer Inc.; Wyeth Inc

Taking the Measure of the Universe: Precision Astrometry with SIM PlanetQuest

Precision astrometry at microarcsecond accuracy has application to a wide range of astrophysical problems. This paper is a study of the science questions that can be addressed using an instrument that delivers parallaxes at about 4 microarcsec on targets as faint as V = 20, differential accuracy of 0.6 microarcsec on bright targets, and with flexible scheduling. The science topics are drawn primarily from the Team Key Projects, selected in 2000, for the Space Interferometry Mission PlanetQuest (SIM PlanetQuest). We use the capabilities of this mission to illustrate the importance of the next level of astrometric precision in modern astrophysics. SIM PlanetQuest is currently in the detailed design phase, having completed all of the enabling technologies needed for the flight instrument in 2005. It will be the first space-based long baseline Michelson interferometer designed for precision astrometry. SIM will contribute strongly to many astronomical fields including stellar and galactic astrophysics, planetary systems around nearby stars, and the study of quasar and AGN nuclei. SIM will search for planets with masses as small as an Earth orbiting in the `habitable zone' around the nearest stars using differential astrometry, and could discover many dozen if Earth-like planets are common. It will be the most capable instrument for detecting planets around young stars, thereby providing insights into how planetary systems are born and how they evolve with time. SIM will observe significant numbers of very high- and low-mass stars, providing stellar masses to 1%, the accuracy needed to challenge physical models. Using precision proper motion measurements, SIM will probe the galactic mass distribution and the formation and evolution of the Galactic halo. (abridged)Comment: 54 pages, 28 figures, uses emulateapj. Submitted to PAS

Triple oxygen isotope insight into terrestrial pyrite oxidation

The mass-independent minor oxygen isotope compositions (Δ′17O) of atmospheric O2 and CO2 are primarily regulated by their relative partial pressures, pO2/pCO2. Pyrite oxidation during chemical weathering on land consumes O2 and generates sulfate that is carried to the ocean by rivers. The Δ′17O values of marine sulfate deposits have thus been proposed to quantitatively track ancient atmospheric conditions. This proxy assumes direct O2 incorporation into terrestrial pyrite oxidation-derived sulfate, but a mechanistic understanding of pyrite oxidation—including oxygen sources—in weathering environments remains elusive. To address this issue, we present sulfate source estimates and Δ′17O measurements from modern rivers transecting the Annapurna Himalaya, Nepal. Sulfate in high-elevation headwaters is quantitatively sourced by pyrite oxidation, but resulting Δ′17O values imply no direct tropospheric O2 incorporation. Rather, our results necessitate incorporation of oxygen atoms from alternative, 17O-enriched sources such as reactive oxygen species. Sulfate Δ′17O decreases significantly when moving into warm, low-elevation tributaries draining the same bedrock lithology. We interpret this to reflect overprinting of the pyrite oxidation-derived Δ′17O anomaly by microbial sulfate reduction and reoxidation, consistent with previously described major sulfur and oxygen isotope relationships. The geologic application of sulfate Δ′17O as a proxy for past pO2/pCO2 should consider both 1) alternative oxygen sources during pyrite oxidation and 2) secondary overprinting by microbial recycling