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At least 379 records · Page 21Linked to original sources

Microbial mass-dependent fractionation of chromium isotopes

Mass-dependent fractionation of Cr isotopes occurs during dissimilatory Cr(VI) reduction by Shewanella oneidensis strain MR-1. Cells suspended in a simple buffer solution, with various concentrations of lactate or formate added as electron donor, reduced 5 or 10 ??M Cr(VI) to Cr(III) over days to weeks. In all nine batch experiments, 53Cr/52Cr ratios of the unreacted Cr(VI) increased as reduction proceeded. In eight experiments covering a range of added donor concentrations up to 100 ??M, isotopic fractionation factors were nearly invariant, ranging from 1.0040 to 1.0045, with a mean value somewhat larger than that previously reported for abiotic Cr(VI) reduction (1.0034). One experiment containing much greater donor concentration (10 mM lactate) reduced Cr(VI) much faster and exhibited a lesser fractionation factor (1.0018). These results indicate that 53Cr/52Cr measurements should be effective as indicators of Cr(VI) reduction, either bacterial or abiotic. However, variability in the fractionation factor is poorly constrained and should be studied for a variety of microbial and abiotic reduction pathways. ?? 2008 Elsevier Ltd.

Geochimica et Cosmochimica Acta

The kinetics of iodide oxidation by the manganese oxide mineral birnessite

The kinetics of iodide (I − ) and molecular iodine (I 2 ) oxidation by the manganese oxide mineral birnessite (δ-MnO 2 ) was investigated over the pH range 4.5–6.25. I − oxidation to iodate ( IO 3 - ) "> (IO3-) proceeded as a two-step reaction through an I 2 intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I − from solution was first order with respect to I − concentration, pH, and birnessite concentration, such that − d [I − ]/ dt = k [I − ][H + ][MnO 2 ], where k , the third order rate constant, is equal to 1.08 ± 0.06 × 10 7 M −2 h −1 . The data are consistent with the formation of an inner sphere I − surface complex as the first step of the reaction, and the adsorption of I − exhibited significant pH dependence. Both I 2 , and to a lesser extent, IO 3 - "> IO3- sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I 2 and IO 3 - "> IO3- , as well as the biophilic nature of I 2 , redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds.

Geochimica et Cosmochimica Acta

Hapke modeling of Rhea surface properties through Cassini-VIMS spectra

T The surface properties of the icy bodies in the saturnian system have been investigated by means of the Cassini-VIMS (Visual Infrared Mapping Spectrometer) hyperspectral imager which operates in the 0.35–5.1 μm wavelength range. In particular, we have analyzed 111 full disk hyperspectral images of Rhea ranging in solar phase between 0.08° and 109.8°. These data have been previously analyzed by Filacchione et al. (Filacchione, G. et al. [2007]. Icarus 186, 259–290; Filacchione, G. et al. [2010]. Icarus 206, 507–523) to study, adopting various “spectral indicators” (such as spectral slopes, band depth, and continuum level), the relations among various saturnian satellites. As a further step we proceed in this paper to a quantitative evaluation of the physical parameters determining the spectrophotometric properties of Rhea’s surface. To do this we have applied Hapke (Hapke, B. [1993]. Theory of Reflectance and Emittance Spectroscopy, Topics in Remote Sensing: 3. Springer, Berlin) IMSA model (Isotropic Multiple Scattering Approximation) which allow us to model the phase function at VIS–IR (visible–infrared) wavelengths as well as the spectra taking into account various types of mixtures of surface materials. Thanks to this method we have been able to constrain the size of water ice particles covering the surface, the amount of organic contaminants, the large scale surface roughness and the opposition effect surge. From our analysis it appears that wavelength dependent parameters, e.g. opposition surge width ( h ) and single-particle phase function parameters ( b , v ), are strongly correlated to the estimated single-scattering albedo of particles. For Rhea the best fit solution is obtained by assuming: (1) an intraparticle mixture of crystalline water ice and a small amount (0.4%) of Triton tholin; (2) a monodisperse grain size distribution having a particle diameter a m = 38 μm; and (3) a surface roughness parameter value of 33°. The study of phase function shows that both shadow hiding and coherent backscattering contribute to the opposition surge. This study represents the first attempt, in the case of Rhea, to join the spectral and the photometric analysis. The surface model we derived gives a good quantitative description of both spectrum and phase curve of the satellite. The same approach and model, with appropriate modifications, shall be applied to VIMS data of the other icy satellites of Saturn, in order to reveal similarities and differences in the surface characteristics to understand how these bodies interact with their environment.

Icarus

6th international conference on Mars polar science and exploration: Conference summary and five top questions

We provide a historical context of the International Conference on Mars Polar Science and Exploration and summarize the proceedings from the 6th iteration of this meeting. In particular, we identify five key Mars polar science questions based primarily on presentations and discussions at the conference and discuss the overlap between some of those questions. We briefly describe the seven scientific field trips that were offered at the conference, which greatly supplemented conference discussion of Mars polar processes and landforms. We end with suggestions for measurements, modeling, and laboratory and field work that were highlighted during conference discussion as necessary steps to address key knowledge gaps.

Icarus

Adaptive management for soil ecosystem services

Ecosystem services provided by soil include regulation of the atmosphere and climate, primary (including agricultural) production, waste processing, decomposition, nutrient conservation, water purification, erosion control, medical resources, pest control, and disease mitigation. The simultaneous production of these multiple services arises from complex interactions among diverse aboveground and belowground communities across multiple scales. When a system is mismanaged, non-linear and persistent losses in ecosystem services can arise. Adaptive management is an approach to management designed to reduce uncertainty as management proceeds. By developing alternative hypotheses, testing these hypotheses and adjusting management in response to outcomes, managers can probe dynamic mechanistic relationships among aboveground and belowground soil system components. In doing so, soil ecosystem services can be preserved and critical ecological thresholds avoided. Here, we present an adaptive management framework designed to reduce uncertainty surrounding the soil system, even when soil ecosystem services production is not the explicit management objective, so that managers can reach their management goals without undermining soil multifunctionality or contributing to an irreversible loss of soil ecosystem services.

Journal of Environmental Management

Use of structured decision-making to explicitly incorporate environmental process understanding in management of coastal restoration projects: Case study on barrier islands of the northern Gulf of Mexico

Coastal ecosystem management typically relies on subjective interpretation of scientific understanding, with limited methods for explicitly incorporating process knowledge into decisions that must meet multiple, potentially competing stakeholder objectives. Conversely, the scientific community lacks methods for identifying which advancements in system understanding would have the highest value to decision-makers. A case in point is barrier island restoration, where decision-makers lack tools to objectively use system understanding to determine how to optimally use limited contingency funds when project construction in this dynamic environment does not proceed as expected. In this study, collaborative structured decision-making (SDM) was evaluated as an approach to incorporate process understanding into mid-construction decisions and to identify priority gaps in knowledge from a management perspective. The focus was a barrier island restoration project at Ship Island, Mississippi, where sand will be used to close an extensive breach that currently divides the island. SDM was used to estimate damage that may occur during construction, and guide repair decisions within the confines of limited availability of sand and funding to minimize adverse impacts to project objectives. Sand was identified as more limiting than funds, and unrepaired major breaching would negatively impact objectives. Repairing minor damage immediately was determined to be generally more cost effective (depending on the longshore extent) than risking more damage to a weakened project. Key gaps in process-understanding relative to project management were identified as the relationship of island width to breach formation; the amounts of sand lost during breaching, lowering, or narrowing of the berm; the potential for minor breaches to self-heal versus developing into a major breach; and the relationship between upstream nourishment and resiliency of the berm to storms. This application is a prototype for using structured decision-making in support of engineering projects in dynamic environments where mid-construction decisions may arise; highlights uncertainty about barrier island physical processes that limit the ability to make robust decisions; and demonstrates the potential for direct incorporation of process-based models in a formal adaptive management decision framework.

Mississippi

An evaluation of fish spawning on degraded and remnant reefs in Saginaw Bay, Lake Huron

Saginaw Bay is a shallow, nutrient-rich embayment in Lake Huron that historically had a complex network of natural rocky reefs. These reef habitats were used as spawning and nursery areas for a variety of fish species, but decades of land-use related sedimentation caused many of these reefs to be degraded. Our study objectives were to analyze abiotic and biotic conditions on degraded and remnant reefs and describe spawning patterns of walleye ( Sander vitreus ) and lake whitefish ( Coregonus clupeaformis ) at these sites to determine the potential for increased utilization following reef restoration. During fall and spring 2014–2016, we evaluated water quality and egg predation at four sites with varying levels of reef degradation. Further, we documented reproductive utilization through capture of spawning adults and quantification of egg deposition. Walleye and lake whitefish utilized multiple sites for reproduction; however, densities of spawners and deposited eggs were low, suggesting that they were not utilizing study sites as major spawning locations. Walleye and lake whitefish eggs were eaten by multiple fish species, including larger fish such as channel catfish ( Ictalurus punctatus ). Dissolved oxygen levels were adequate (i.e., >7 mg 0 2 L −1 ) during spring walleye egg incubation; however, bottom dissolved oxygen levels became very low at some sites during winter ice cover, coinciding with lake whitefish egg incubation. As restoration of rocky reefs proceeds in the Bay, evidence of remnant reef spawning fish bodes well for long-term success, though potential limiting factors such as low dissolved oxygen, sedimentation, and egg predation require continued monitoring.

Michigan

The Lepanto Cu–Au deposit, Philippines: A fossil hyperacidic volcanic lake complex

Hyperacidic lakes and associated solfatara in active volcanoes are the expression of magmatic gas expansion from source to surface. Here we show for the first time, that the vein system that comprises the ~ 2 Ma high-sulfidation, Lepanto copper–gold deposit in the Mankayan district (Philippines) was associated with a contemporary hyperacidic volcanic lake complex—possibly the first such lake recognized in the geological record. A 15–20‰ difference in sulfur isotopic composition between barite and sulfides and sulfosalts in the vent fumarole encrustations supports the interpretation that SO 2 -rich volcanic gas vented into the base of the lake and marginal to it and ties the mineralization directly to magmatic gas expansion, fracture propagation, and mineralization that occurred through a series of decompression steps within the feeder fracture network. These data confirm that crater lake environments such as Kawah Ijen (Java, Indonesia) provide modern day analogs of the Lepanto and other high sulfidation Cu–Au depositing environments. We also provide extensive analysis of sulfosalt–sulfide reactions during vein formation within the hyperacidic lake complex. Pyrite ± silica deposited first at high temperature followed by enargite that preserves the vapor–solid diffusion of, for example, antimony, tin, and tellurium into the vapor from the crystallizing solid. Subsolidus, intra-crystalline diffusion continued as temperature declined. Pyrite and enargite are replaced by Fe-tennantite in the lodes which initially has low Sb/(Sb + As) atomic ratios around 13.5% close to the ideal tennantite formula, but evolves to higher ratios as crystallization proceeds. Fumarole encrustation clasts and sulfosalts in the lake sediment are more highly evolved with a larger range of trace element substitutions, including antimony. Substitution of especially Zn, Te, Ag, and Sn into tennantite records metal and semi-metal fractionation between the expanding magmatic gas and deposited sulfide sublimates provides a rare insight into the fate of metals and semi-metals in the shallower parts of fracture arrays that feed modern hyperacidic lakes. These data support a growing understanding of the formation of high-sulfidation gold deposits as the consequence of single-phase expansion of gas from magmatic-gas reservoirs beneath the surface of active volcanoes without the intervention of a later aqueous fluid including groundwater. Aggressive sulfide–sulfosalt reactions, including pitting and the almost complete dissolution of earlier minerals, are persistent characteristics of the vein assemblages and precious metals typically occur late in pits or along brittle fractures. These characteristics support a hypothesis of mineral deposition at temperatures of the order of 600 °C in contrast to available fluid inclusion data from enargite that record temperatures following phase transitions in the sulfosalt during the retrograde devolution of the deposit in the presence of groundwater.

Benguet

Characterizing unrest: A retrospective look at 20 years of gas emissions and seismicity at Iliamna Volcano, Alaska

Episodes of unrest are not as well documented as eruptions at most volcanoes globally. Iliamna is an andesitic stratovolcano in the Cook Inlet of Alaska that has experienced several episodes of unrest. Unrest in 1996 was previously studied. Here we present data from a minor period of unrest between 2002 and 2006, and a more significant period in 2012. None of the episodes led to an eruption. A dike intrusion was suggested for the 1996 unrest based on increases in gas emissions and seismic analysis. The 2002–2006 period was characterized by a slight increase in the rate of seismicity to 13 events per day and was particularly notable due to an increase in deep long period (DLP) seismic events between 15 and 37 km that were not observed at other times. This period also included one airborne gas measurement with and elevated CO 2 /SO 2 molar ratio (17). In 2012, Iliamna unrest was characterized by significantly elevated gas emissions (up to 582 t/d SO 2 and 1385 t/d CO 2 ) and up to 49 located earthquakes per day (M > 0), and was remarkably similar to the 1996 unrest. Differences in the observed evolution of the CO 2 /SO 2 gas ratio in 2012 (2.2–4) compared to that in 1996 (up to 18) suggests that no new deep magma was involved in 2012, however this does not preclude the movement of a previously intruded magma. A months-long increase in the SO 2 /H 2 S molar ratio from 8 to 17 during the peak of the activity could reflect a temperature increase on the order of 10–30 °C of the emitted gas. Compared to pre-eruptive unrest at other Cook Inlet volcanoes, Iliamna unrest in 2012 differed in that gas emissions were < 1500 t/d and seismicity lacked a rapidly escalating sequence of earthquakes and volcanic tremor, which is normally observed in the hours to days before eruption. The observation of DLPs, the fact that Iliamna produces moderately elevated degassing over decadal timeframes, and the persistent dominance of SO 2 over H 2 S, suggests that periodic input of fresh magma from the lower crust sustains the shallower magmatic system over time, which sets it apart from neighboring volcanoes in the Cook Inlet that show minimal activity between eruptions. Various scenarios could explain why Iliamna did not proceed to eruption in 2012. Finally, we present criteria by which monitoring data may suggest an increased likelihood of eruption at Iliamna in the future.

Alaska

Geologic framework of the 2005 Keathley Canyon gas hydrate research well, northern Gulf of Mexico

The Keathley Canyon sites drilled in 2005 by the Chevron Joint Industry Project are located along the southeastern edge of an intraslope minibasin (Casey basin) in the northern Gulf of Mexico at 1335 m water depth. Around the drill sites, a grid of 2D high-resolution multichannel seismic data designed to image depths down to at least 1000 m sub-bottom reveals 7 unconformities and disconformities that, with the seafloor, bound 7 identifiable seismic stratigraphic units. A major disconformity in the middle of the units stands out for its angular baselapping geometry. From these data, three episodes of sedimentary deposition and deformation are inferred. The oldest episode consists of fine-grained muds deposited during a period of relative stability in the basin (units e, f, and g). Both the BSR and inferred gas hydrate occur within these older units. The gas hydrate occurs in near-vertical fractures. A second episode (units c and d) involved large vertical displacements associated with infilling and ponding of sediment. This second interval corresponds to deposition of intercalated fine and coarse-grained material that was recovered in the drill hole that penetrated the thin edges of the regionally much thicker units. The final episode of deposition (units a and b) occurred during more subdued vertical motions. Hemipelagic drape (unit a) characterizes the modern seafloor. The present-day Casey basin is mostly filled. Its sill is part of a subsiding graben structure that is only 10-20 m shallower than the deepest point in the basin, indicating that gravity-driven transport would mostly bypass the basin. Contemporary faulting along the basin margins has selectively reactivated an older group of faults. The intercalated sand and mud deposits of units c and d are tentatively correlated with Late Pleistocene deposition derived from the western shelf-edge delta/depocenter of the Mississippi River, which was probably most active from 320 ka to 70 ka [Winker, C.D., Booth, J., 2000. Sedimentary dynamics of the salt-dominated continental slope, Gulf of Mexico: integration of observations from the seafloor, near-surface, and deep subsurface. In: Proceedings of the GCSSEPM Foundation 20th Annual Research Conference, Deep-water Reservoirs of the World, pp. 1059-1086]. The presence of sand within the gas hydrate stability zone (in units c and d) is not sufficient to concentrate gas hydrate even though dispersed gas hydrate occurs deeper in the fractured mud/clay-rich sections of units e and f.

Gulf of Mexico

Apatite trace element geochemistry and cathodoluminescent textures—Acomparison between regional magmatism and the Pea Ridge IOA-REE andBoss IOCG deposits, southeastern Missouri iron metallogenic province, USA

The southeast Missouri iron metallogenic province contains a remarkable wealth of historically important Fe, Cu, Au, and rare earth element (REE) deposits including the Pea Ridge iron oxide-apatite-rare earth element (IOA-REE) deposit and the Boss iron oxide-copper-gold (IOCG) deposit. These deposits are coeval with silicic and intermediate composition magmatism in the St. Francois Mountains terrane. Magmatism, iron-oxide (±Cu, Au, Co) and apatite formation, and REE mineralization overlapped in space and time, but the specific role of regional magmatism in the metallogenesis of these deposits remains unclear and basic petrogenetic models are still debated. We report results from high-spatial resolution textural and geochemical analyses of apatite from regional igneous and ore rocks to elucidate their petrogenetic histories and evaluate deposit models. Backscattered electron and spectral cathodoluminescence imaging of apatite reveal no primary igneous zoning, but show different domains with intricate rims and dissolution/reprecipitation textures, each with distinctive REE patterns in many samples. Apatite from all samples are nearly endmember fluorapatite containing up to ~1.3 wt% Cl and F/Cl ratios span nearly three orders of magnitude. Fresh igneous fluorapatite contain low Na2O (0.15 wt%) while most Pea Ridge ore samples contain higher Na2O (up to ~0.45 wt%), and concentrations of sulfur in fluorapatite of all types are generally moderate to low (0.3 wt% SO3). Significant amounts of Fe (60,000 ppm), Mg (30,000 ppm), Mn (7,000 ppm), and Sr (12,000 ppm) are contained in fluorapatite of all sample types, and they also have moderate amounts of As (4,000 ppm), Ba (2,000 ppm), Th (400 ppm), and U (80 ppm). Fluorapatite show an extraordinarily large range of REE (~0.1-2.0 wt%) and Y (~100-7000 ppm) concentrations. While fresh igneous fluorapatite share many geochemical features with metasomatized igneous fluorapatite and ore-stage fluorapatite from the Pea Ridge IOA and Boss IOCG ore zones, they also have distinct geochemical signatures that are indicative of unique trace element partitioning and substitution mechanisms. These distinguishing textural and geochemical signatures preclude ore-zone fluorapatite genesis directly from a magma (i.e., crystallization directly from a silicate melt) but are permissive of ore-zone fluorapatite formation by magmatic-hydrothermal fluids derived from the regional magmas. Basinal brines may play an important role in the formation of fluorapatite, especially from the Pea Ridge hematite and Boss magnetite-rich zones. Fluorapatite from different ore zones likely formed by crystallization during pulses of hydrothermal fluids with varying Cl-, Na-, and F-contents, which fundamentally controlled the carrying capacity and solubility of REE+Y and generated geochemically distinctive generations of fluorapatite. Exploration geologists using fluorapatite trace element geochemistry to identify IOA and IOCG deposits should proceed with caution, as more high-quality data from these deposits are needed to improve multivariate discrimination analysis. Fluorapatite from IOA/IOCG deposits can be reasonably discriminated from that of other mineral deposit types (e.g., porphyry/epithermal, skarn, orogenic), but no criteria successfully discriminate yet between IOA and IOCG deposits.

Missouri

Microtextural evidence for the recrystallization of opal-A to quartz in epithermal veins: A case study from the McLaughlin deposit, California

High-grade ores in low-sulfidation epithermal deposits commonly consist of banded veins containing quartz as the most abundant gangue mineral. Previous studies suggested that at least some of the quartz has formed as a product of recrystallization from a noncrystalline silica precursor. Detailed petrographic studies confirm that high-grade veins from the <2.2 Ma McLaughlin deposit in California were originally entirely composed of opal-A G . The noncrystalline silica is isotropic in crossed-polarized light and consists of compacted microspheres that are up to several micrometers in size. In many bands of the high-grade veins, the thermodynamically unstable opal-A G has matured to quartz. The recrystallization of the noncrystalline silica resulted in the development of quartz and ore textures that mask the original conditions of vein formation. Incipient recrystallization of the opal-A G caused the formation of lepispheres consisting of opal-CT as well as the development of concentrically banded silica spheres. Continued maturation led to the growth of elongated quartz crystals or complexly shaped quartz aggregates in the cores of the concentrically banded silica spheres. Amalgamation of quartz crystals caused the development of mosaic quartz or flamboyant quartz. Ripening produced large prismatic quartz crystals, which are characterized by zones of feathery appearance. Fluid inclusions within the quartz formed through recrystallization are typically highly irregular in shape and show inconsistent liquid-to-vapor volumetric proportions, but assemblages with consistent ratios are also present. Bands rich in fluid inclusions occurring along former recrystallization fronts in prismatic quartz crystals resemble growth zones in zonal quartz. Recrystallization of the silica matrix resulted in grain coarsening of the ore minerals and encapsulation of ore minerals by quartz. In areas where recrystallization of the noncrystalline silica proceeded to completeness, the quartz textures could be easily misinterpreted to indicate that quartz growth occurred in open space with the ore minerals infilling vug spaces. Correct recognition of recrystallization textures has significant implications for paragenetic investigations on vein material from epithermal deposits as well as the design of fluid inclusion studies.

California

Fifty years of IMOG (International Meetings on Organic Geochemistry)

IMOG2011 is the 25th of a series of international meetings on organic geochemistry that began in 1962. Thus, this 25th meeting marks the 50th anniversary year of IMOG, which has (a) had a rich history with meetings taking place in 11 different countries, (b) published Proceedings, titled “Advances in Organic Geochemistry,” from each meeting that now number 24 volumes totaling almost 18,000 pages, and (c) documented the content and development of the science of organic geochemistry. IMOG2011 adds a new milestone to the progress of organic geochemistry through time.

Organic Geochemistry

Browsing the literature

For this edition of Browsing the Literature, we have two new papers from Rangeland Ecology & Management, a series of basic ecology papers with an international scope from journals such as the Proceedings of the National Academy of Sciences (USA), Science, and Nature, and several papers advancing our understanding of drought and carbon at global scales. Additionally, several papers on sagebrush-steppe rangelands are covered with transferable insights to other rangeland types.

Rangelands

Holistic assessment of occurrence and fate of metolachlor within environmental compartments of agricultural watersheds

Background : Metolachlor [(RS)-2-Chloro- N -(2-ethyl-6-methyl-phenyl)- N -(1-methoxypropan-2-yl)acetamide] and two degradates (metolachlor ethane-sulfonic acid and metolachlor oxanilic acid) are commonly observed in surface and groundwater. The behavior and fate of these compounds were examined over a 12-year period in seven agricultural watersheds in the United States. They were quantified in air, rain, streams, overland flow, groundwater, soil water, subsurface drain water, and water at the stream/groundwater interface. The compounds were frequently detected in surface and groundwater associated with agricultural areas. A mass budget approach, based on all available data from the study and literature, was used to determine a percentage-wise generalized distribution and fate of applied parent metolachlor in typical agricultural environments. Results : In these watersheds, about 90% of applied metolachlor was taken up by plants or degraded, 10% volatilized, and 0.3% returned as rainfall. One percent was transported to surface water, while an equal amount infiltrated into the unsaturated zone soil water. < 0.02% reached the groundwater. Subsurface flow paths resulted in greater degradation of metolachlor because degradation reactions had more time to proceed. Conclusions : An understanding of the residence times of water in the different environmental compartments, and the important processes affecting metolachlor as it is transported along flowpaths among the environmental compartments allows for a degree of predictability of metolachlor's fate. Degradates with long half-lives can be used (in a limited capacity) as tracers of metolachlor, because of their persistence and widespread occurrence in the environment.

Science of the Total Environment

De facto water reuse: Bioassay suite approach delivers depth and breadth in endocrine active compound detection

Although endocrine disrupting compounds (EDCs) have been detected in wastewater and surface waters worldwide using a variety of in vitro effects-based screening tools, e.g. bioassays, few have examined potential attenuation of environmental contaminants by both natural (sorption, degradation, etc) and anthropogenic (water treatment practices) processes. This study used several bioassays and quantitative chemical analyses to assess residence-time weighted samples at six sites along a river in the northeastern United States beginning upstream of a waste water treatment plant (WWTP) outfall and proceeding downstream along the stream reach to a drinking water treatment plant (DWTP). Known steroidal estrogens were quantified and changes in signaling pathway molecular initiating events (activation of estrogen, androgen, glucocorticoid, peroxisome proliferator-activated, pregnane X receptor, and aryl hydrocarbon receptor signaling networks) were identified in water extracts. In initial multi-endpoint assays geographic and receptor-specific endocrine activity patterns in transcription factor signatures and nuclear receptor activation were discovered. In subsequent single endpoint receptor-specific bioassays, estrogen (16 of 18 samples; 0.01 to 28 ng estradiol equivalents [E2Eqs]/L) glucocorticoid (3 of 18 samples; 1.8 to 21 ng dexamethasone equivalents [DexEqs]/L), and androgen (2 of 18 samples; 0.95 to 2.1 ng dihydrotestosterone equivalents [DHTEqs]/L) receptor transcriptional activation occurred above respective assay method detection limits (0.04 ng E2Eqs/L, 1.2 ng DexEqs/L, and 0.77 ng DHTEqs/L) in multiple sampling events. Estrogen activity, the most often detected, correlated well with measured concentrations of known steroidal estrogens (R2 = 0.890). Overall, activity indicative of multiple types of endocrine active compounds was highest in wastewater effluent samples, while activity downstream was progressively lower, and negligible in (unfinished) treated water. This multiple bioassay approach, in conjunction with targeted analytical chemistry methods, has gained acceptance among water quality screening programs. Not only was estrogenic and glucocorticoid activity confirmed in the effluent by utilizing multiple methods concurrently, but other activated signaling networks that historically received less attention (i.e. peroxisome proliferator-activated receptor) were also detected.

Science of the Total Environment

Animal movement models with mechanistic selection functions

A suite of statistical methods are used to study animal movement. Most of these methods treat animal trajectory data in one of three ways: as discrete pro- cesses, as continuous processes, or as point processes. We brie y review each of these approaches and then focus in on the latter. In the context of point processes, so-called resource selection analyses are among the most common way to statis- tically treat animal trajectory data. However, most resource selection analyses provide inference based on approximations of point process models. The forms of these models have been limited to a few types of specications that provide infer- ence about relative resource use and, less commonly, probability of use. For more general spatio-temporal point process models, the most common type of analysis often proceeds with a data augmentation approach that is used to create a binary data set that can be analyzed with conditional logistic regression. We show that the conditional logistic regression likelihood can be generalized to accommodate a variety of alternative specications related to resource selection. We then provide an example of a case where a spatio-temporal point process model coincides with that implied by a mechanistic model for movement expressed as a partial dier- ential equation derived from rst principles of movement. We demonstrate that inference from this form of point process model is intuitive (and could be useful for management and conservation) by analyzing a set of telemetry data from a mountain lion in Colorado, USA, to understand the eects of spatially explicit environmental conditions on movement behavior of this species.

Spatial Statistics

Kinetics of the coesite to quartz transformation

The survival of coesite in ultrahigh-pressure (UHP) rocks has important implications for the exhumation of subducted crustal rocks. We have conducted experiments to study the mechanism and rate of the coesite→quartz transformation using polycrystalline coesite aggregates, fabricated by devitrifying silica glass cylinders containing 2850 H/10 6 Si at 1000°C and 3.6 GPa for 24 h. Conditions were adjusted following synthesis to transform the samples at 700–1000°C at pressures 190–410 MPa below the quartz–coesite equilibrium boundary. Reaction proceeds via grain-boundary nucleation and interface-controlled growth, with characteristic reaction textures remarkably similar to those seen in natural UHP rocks. We infer that the experimental reaction mechanism is identical to that in nature, a prerequisite for reliable extrapolation of the rate data. Growth rates obtained by direct measurement differ by up to two orders of magnitude from those estimated by fitting a rate equation to the transformation–time data. Fitting the rates to Turnbull's equation for growth therefore yields two distinct sets of parameters with similar activation energies (242 or 269 kJ/mol) but significantly different pre-exponential constants. Extrapolation based on either set of growth rates suggests that coesite should not be preserved on geologic time scales if it reaches the quartz stability field at temperatures above 375–400°C. The survival of coesite has previously been linked to its inclusion in strong phases, such as garnet, that can sustain a high internal pressure during decompression. Other factors that may play a crucial role in preservation are low fluid availability — possibly even less than that of our nominally “dry” experiments — and the development of transformation stress, which inhibits nucleation and growth. These issues are discussed in the context of our experiments as well as recent observations from natural rocks.

Earth and Planetary Science Letters