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Developing a set of indicators to identify, monitor, and track impacts and change in forests of the United States

United States forestland is an important ecosystem type, land cover, land use, and economic resource that is facing several drivers of change including climatic. Because of its significance, forestland was identified through the National Climate Assessment (NCA) as a key sector and system of concern to be included in a system of climate indicators as part of a sustained assessment effort. Here, we describe 11 informative core indicators of forests and climate change impacts with metrics available or nearly available for use in the NCA efforts. The recommended indicators are based on a comprehensive conceptual model which recognizes forests as a land use, an ecosystem, and an economic sector. The indicators cover major forest attributes such as extent, structural components such as biomass, functions such as growth and productivity, and ecosystem services such as biodiversity and outdoor recreation. Interactions between humans and forests are represented through indicators focused on the wildland-urban interface, cost to mitigate wildfire risk, and energy produced from forest-based biomass. Selected indicators also include drought and disturbance from both wildfires and biotic agents. The forest indicators presented are an initial set that will need further refinement in coordination with other NCA indicator teams. Our effort ideally will initiate the collection of critical measurements and observations and lead to additional research on forest-climate indicators.

Climatic Change↗

Anticoagulant rodenticides in urban bobcats: exposure, risk factors and potential effects based on a 16-year study

Anticoagulant rodenticides (ARs) are increasingly recognized as a threat to nontarget wildlife. High exposure to ARs has been documented globally in nontarget predatory species and linked to the high prevalence of an ectoparasitic disease, notoedric mange. In southern California, mange associated with AR exposure has been the proximate cause of a bobcat ( Lynx rufus ) population decline. We measured AR exposure in bobcats from two areas in southern California, examining seasonal, demographic and spatial risk factors across landscapes including natural and urbanized areas. The long-term study included bobcats sampled over a 16-year period (1997–2012) and a wide geographic area. We sampled blood ( N = 206) and liver ( N = 172) to examine exposure ante- and post-mortem. We detected high exposure prevalence (89 %, liver; 39 %, blood) and for individuals with paired liver and blood data ( N = 64), 92 % were exposed. Moreover, the animals with the most complete sampling were exposed most frequently to three or more compounds. Toxicant exposure was associated with commercial, residential, and agricultural development. Bobcats of both sexes and age classes were found to be at high risk of exposure, and we documented fetal transfer of multiple ARs. We found a strong association between certain levels of exposure (ppm), and between multiple AR exposure events, and notoedric mange. AR exposure was prevalent throughout both regions sampled and throughout the 16-year time period in the long-term study. ARs pose a substantial threat to bobcats, and likely other mammalian and avian predators, living at the urban-wildland interface.

Ecotoxicology↗

Representing general theoretical concepts in structural equation models: The role of composite variables

Structural equation modeling (SEM) holds the promise of providing natural scientists the capacity to evaluate complex multivariate hypotheses about ecological systems. Building on its predecessors, path analysis and factor analysis, SEM allows for the incorporation of both observed and unobserved (latent) variables into theoretically-based probabilistic models. In this paper we discuss the interface between theory and data in SEM and the use of an additional variable type, the composite. In simple terms, composite variables specify the influences of collections of other variables and can be helpful in modeling heterogeneous concepts of the sort commonly of interest to ecologists. While long recognized as a potentially important element of SEM, composite variables have received very limited use, in part because of a lack of theoretical consideration, but also because of difficulties that arise in parameter estimation when using conventional solution procedures. In this paper we present a framework for discussing composites and demonstrate how the use of partially-reduced-form models can help to overcome some of the parameter estimation and evaluation problems associated with models containing composites. Diagnostic procedures for evaluating the most appropriate and effective use of composites are illustrated with an example from the ecological literature. It is argued that an ability to incorporate composite variables into structural equation models may be particularly valuable in the study of natural systems, where concepts are frequently multifaceted and the influence of suites of variables are often of interest. ?? Springer Science+Business Media, LLC 2007.

Environmental and Ecological Statistics↗

A data-based conservation planning tool for Florida panthers

Habitat loss and fragmentation are the greatest threats to the endangered Florida panther ( Puma concolor coryi ). We developed a data-based habitat model and user-friendly interface so that land managers can objectively evaluate Florida panther habitat. We used a geographic information system (GIS) and the Mahalanobis distance statistic ( D 2 ) to develop a model based on broad-scale landscape characteristics associated with panther home ranges. Variables in our model were Euclidean distance to natural land cover, road density, distance to major roads, human density, amount of natural land cover, amount of semi-natural land cover, amount of permanent or semi-permanent flooded area–open water, and a cost–distance variable. We then developed a Florida Panther Habitat Estimator tool, which automates and replicates the GIS processes used to apply the statistical habitat model. The estimator can be used by persons with moderate GIS skills to quantify effects of land-use changes on panther habitat at local and landscape scales. Example applications of the tool are presented.

Florida↗

The ChemCam Instrument Suite on the Mars Science Laboratory (MSL) Rover: Science objectives and mast unit description

ChemCam is a remote sensing instrument suite on board the "Curiosity" rover (NASA) that uses Laser-Induced Breakdown Spectroscopy (LIBS) to provide the elemental composition of soils and rocks at the surface of Mars from a distance of 1.3 to 7 m, and a telescopic imager to return high resolution context and micro-images at distances greater than 1.16 m. We describe five analytical capabilities: rock classification, quantitative composition, depth profiling, context imaging, and passive spectroscopy. They serve as a toolbox to address most of the science questions at Gale crater. ChemCam consists of a Mast-Unit (laser, telescope, camera, and electronics) and a Body-Unit (spectrometers, digital processing unit, and optical demultiplexer), which are connected by an optical fiber and an electrical interface. We then report on the development, integration, and testing of the Mast-Unit, and summarize some key characteristics of ChemCam. This confirmed that nominal or better than nominal performances were achieved for critical parameters, in particular power density (>1 GW/cm 2 ). The analysis spot diameter varies from 350 μm at 2 m to 550 μm at 7 m distance. For remote imaging, the camera field of view is 20 mrad for 1024×1024 pixels. Field tests demonstrated that the resolution (˜90 μrad) made it possible to identify laser shots on a wide variety of images. This is sufficient for visualizing laser shot pits and textures of rocks and soils. An auto-exposure capability optimizes the dynamical range of the images. Dedicated hardware and software focus the telescope, with precision that is appropriate for the LIBS and imaging depths-of-field. The light emitted by the plasma is collected and sent to the Body-Unit via a 6 m optical fiber. The companion to this paper (Wiens et al. this issue) reports on the development of the Body-Unit, on the analysis of the emitted light, and on the good match between instrument performance and science specifications.

Space Science Reviews↗

The Mars 2020 Perseverance rover mast camera zoom (Mastcam-Z) multispectral, stereoscopic imaging investigation

Mastcam-Z is a multispectral, stereoscopic imaging investigation on the Mars 2020 mission’s Perseverance rover. Mastcam-Z consists of a pair of focusable, 4:1 zoomable cameras that provide broadband red/green/blue and narrowband 400-1000 nm color imaging with fields of view from 25.6° × 19.2° (26 mm focal length at 283 μrad/pixel) to 6.2° × 4.6° (110 mm focal length at 67.4 μrad/pixel). The cameras can resolve (≥ 5 pixels) ∼0.7 mm features at 2 m and ∼3.3 cm features at 100 m distance. Mastcam-Z shares significant heritage with the Mastcam instruments on the Mars Science Laboratory Curiosity rover. Each Mastcam-Z camera consists of zoom, focus, and filter wheel mechanisms and a 1648 × 1214 pixel charge-coupled device detector and electronics. The two Mastcam-Z cameras are mounted with a 24.4 cm stereo baseline and 2.3° total toe-in on a camera plate ∼2 m above the surface on the rover’s Remote Sensing Mast, which provides azimuth and elevation actuation. A separate digital electronics assembly inside the rover provides power, data processing and storage, and the interface to the rover computer. Primary and secondary Mastcam-Z calibration targets mounted on the rover top deck enable tactical reflectance calibration. Mastcam-Z multispectral, stereo, and panoramic images will be used to provide detailed morphology, topography, and geologic context along the rover’s traverse; constrain mineralogic, photometric, and physical properties of surface materials; monitor and characterize atmospheric and astronomical phenomena; and document the rover’s sample extraction and caching locations. Mastcam-Z images will also provide key engineering information to support sample selection and other rover driving and tool/instrument operations decisions.

Space Science Reviews↗

Transport of viruses through saturated and unsaturated columns packed with sand

Laboratory-scale virus transport experiments were conducted in columns packed with sand under saturated and unsaturated conditions. The viruses employed were the male-specific RNA coliphage, MS2, and the Salmonella typhimurium phage, PRD1. The mathematical model developed by Sim and Chrysikopoulos (Water Resour Res 36:173–179, 2000) that accounts for processes responsible for removal of viruses during vertical transport in one-dimensional, unsaturated porous media was used to fit the data collected from the laboratory experiments. The liquid to liquid–solid and liquid to air–liquid interface mass transfer rate coefficients were shown to increase for both bacteriophage as saturation levels were reduced. The experimental results indicate that even for unfavorable attachment conditions within a sand column (e.g., phosphate-buffered saline solution; pH = 7.5; ionic strength = 2 mM), saturation levels can affect virus transport through porous media.

Transport in Porous Media↗

Mercury and methylmercury dynamics in a coastal plain watershed, New Jersey, USA

The upper Great Egg Harbor River watershed in New Jersey's Coastal Plain is urbanized but extensive freshwater wetlands are present downstream. In 2006-2007, studies to assess levels of total mercury (THg) found concentrations in unfiltered streamwater to range as high as 187 ng/L in urbanized areas. THg concentrations were <20 ng/L in streamwater in forested/wetlands areas where both THg and dissolved organic carbon concentrations tended to increase while pH and concentrations of dissolved oxygen and nitrate decreased with flushing of soils after rain. Most of the river's flow comes from groundwater seepage; unfiltered groundwater samples contained up to 177 ng/L of THg in urban areas where there is a history of well water with THg that exceeds the drinking water standard (2,000 ng/L). THg concentrations were lower (<25 ng/L) in unfiltered groundwater from downstream wetland areas. In addition to higher THg concentrations (mostly particulate), concentrations of chloride were higher in streamwater and groundwater from urban areas than in those from downstream wetland areas. Methylmercury (MeHg) concentrations in unfiltered streamwater ranged from 0.17 ng/L at a forest/wetlands site to 2.94 ng/L at an urban site. The percentage of THg present as MeHg increased as the percentage of forest + wetlands increased, but also was high in some urban areas. MeHg was detected only in groundwater <1 m below the water/sediment interface. Atmospheric deposition is presumed to be the main source of Hg to the wetlands and also may be a source to groundwater, where wastewater inputs in urban areas are hypothesized to mobilize Hg deposited to soils. ?? 2010 US Government.

Water, Air, & Soil Pollution↗

Response and resilience of Spartina alterniflora to sudden dieback

We measured an array of biophysical and spectral variables to evaluate the response and recovery of Spartina alterniflora to a sudden dieback event in spring and summer 2004 within a low marsh in coastal Virginia, USA. S. alterniflora is a foundation species, whose loss decreases ecosystem services and potentiates ecosystem state change. Long-term records of the potential environmental drivers of dieback such as precipitation and tidal inundation did not evidence any particular anomalies, although Hurricane Isabel in fall 2003 may have been related to dieback. Transects were established across the interface between the dieback area and apparently healthy areas of marsh. Plant condition was classified based on ground cover within transects as dieback, intermediate and healthy. Numerous characteristics of S. alterniflora culms within each condition class were assessed including biomass, morphology and spectral attributes associated with photosynthetic pigments. Plants demonstrated evidence of stress in 2004 and 2005 beyond areas of obvious dieback and resilience at a multi-year scale. Resilience of the plants was evident in recovery of ground cover and biomass largely within 3 y, although a small remnant of dieback persisted for 8 y. Culms surviving within the dieback and areas of intermediate impact had modified morphological traits and spectral response that reflected stress. These morphometric and spectral differences among plant cover condition classes serve as guidelines for monitoring of dieback initiation, effects and subsequent recovery. Although a number of environmental and biotic parameters were assessed relative to causation, the reason for this particular dieback remains largely unknown, however.

Virginia↗

Lateral baroclinic forcing enhances sediment transport from shallows to channel in an estuary

We investigate the dynamics governing exchange of sediment between estuarine shallows and the channel based on field measurements at eight stations spanning the interface between the channel and the extensive eastern shoals of South San Francisco Bay. The study site is characterized by longitudinally homogeneous bathymetry and a straight channel, with friction more important than the Coriolis forcing. Data were collected for 3 weeks in the winter and 4 weeks in the late summer of 2009, to capture a range of hydrologic and meteorologic conditions. The greatest sediment transport from shallows to channel occurred during a pair of strong, late-summer wind events, with westerly winds exceeding 10 m/s for more than 24 h. A combination of wind-driven barotropic return flow and lateral baroclinic circulation caused the transport. The lateral density gradient was produced by differences in temperature and suspended sediment concentration (SSC). During the wind events, SSC-induced vertical density stratification limited turbulent mixing at slack tides in the shallows, increasing the potential for two-layer exchange. The temperature- and SSC-induced lateral density gradient was comparable in strength to salinity-induced gradients in South Bay produced by seasonal freshwater inflows, but shorter in duration. In the absence of a lateral density gradient, suspended sediment flux at the channel slope was directed towards the shallows, both in winter and during summer sea breeze conditions, indicating the importance of baroclinically driven exchange to supply of sediment from the shallows to the channel in South San Francisco Bay and systems with similar bathymetry.

California↗

The role of ocean tides on groundwater-surface water exchange in a mangrove-dominated estuary: Shark River Slough, Florida Coastal Everglades, USA

Low-relief environments like the Florida Coastal Everglades (FCE) have complicated hydrologic systems where surface water and groundwater processes are intimately linked yet hard to separate. Fluid exchange within these lowhydraulic-gradient systems can occur across broad spatial and temporal scales, with variable contributions to material transport and transformation. Identifying and assessing the scales at which these processes operate is essential for accurate evaluations of how these systems contribute to global biogeochemical cycles. The distribution of 222 Rn and 223,224,226 Ra have complex spatial patterns along the Shark River Slough estuary (SRSE), Everglades, FL. High-resolution time-series measurements of 222 Rn activity, salinity, and water level were used to quantify processes affecting radon fluxes out of the mangrove forest over a tidal cycle. Based on field data, tidal pumping through an extensive network of crab burrows in the lower FCE provides the best explanation for the high radon and fluid fluxes. Burrows are irrigated during rising tides when radon and other dissolved constituents are released from the mangrove soil. Flushing efficiency of the burrows&mdash;defined as the tidal volume divided by the volume of burrows&mdash; estimated for the creek drainage area vary seasonally from 25 (wet season) to 100 % (dry season) in this study. The tidal pumping of the mangrove forest soil acts as a significant vector for exchange between the forest and the estuary. Processes that enhance exchange of O2 and other materials across the sediment-water interface could have a profound impact on the environmental response to larger scale processes such as sea level rise and climate change. Compounding the material budgets of the SRSE are additional inputs from groundwater from the Biscayne Aquifer, which were identified using radium isotopes. Quantification of the deep groundwater component is not obtainable, but isotopic data suggest a more prevalent signal in the dry season. These findings highlight the important role that both tidal- and seasonal-scale forcings play on groundwater movement in low-gradient hydrologic systems.

Florida↗

Impacts of coastal land use and shoreline armoring on estuarine ecosystems: An introduction to a special issue

The nearshore land-water interface is an important ecological zone that faces anthropogenic pressure from development in coastal regions throughout the world. Coastal waters and estuaries like Chesapeake Bay receive and process land discharges loaded with anthropogenic nutrients and other pollutants that cause eutrophication, hypoxia, and other damage to shallow-water ecosystems. In addition, shorelines are increasingly armored with bulkhead (seawall), riprap, and other structures to protect human infrastructure against the threats of sea-level rise, storm surge, and erosion. Armoring can further influence estuarine and nearshore marine ecosystem functions by degrading water quality, spreading invasive species, and destroying ecologically valuable habitat. These detrimental effects on ecosystem function have ramifications for ecologically and economically important flora and fauna. This special issue of Estuaries and Coasts explores the interacting effects of coastal land use and shoreline armoring on estuarine and coastal marine ecosystems. The majority of papers focus on the Chesapeake Bay region, USA, where 50 major tributaries and an extensive watershed (~ 167,000 km 2 ), provide an ideal model to examine the impacts of human activities at scales ranging from the local shoreline to the entire watershed. The papers consider the influence of watershed land use and natural versus armored shorelines on ecosystem properties and processes as well as on key natural resources.

Estuaries and Coasts↗

Presence of hummock and hollow microtopography reflects shifting balances of shallow subsidence and root zone expansion along forested wetland river gradients

Tidal freshwater forested wetlands (TFFWs) are in an active phase of transition to tidal marsh with sea level rise and salinity incursion along the Atlantic and Gulf Coasts of the United States (U.S.). A prominent feature of TFFWs is hummock/hollow microtopography where hollows represent the flat, base-elevation of the floodplain where inundation occurs relatively frequently, while hummocks provide elevated soil surfaces that often harbor relatively greater numbers and species of trees and shrubs. Hummocks appear at the landscape river boundary just seaward of bottomland hardwoods as tides reach those positions, persist for many years, and disappear as TFFWs eventually transition to marsh. We studied TFFW surface elevation processes along four Atlantic coastal landscape river gradients by using surface elevation tables and marker horizons. Shallow subsidence between trees, equating to as much as 5.5 mm/year, was an important process in hollow maintenance as roots held hummock elevations relatively more stable. However, hummocks were actively subsiding on all sites with little sign of root zone expansion within hummocks, despite hummock elevation gain on some sites. For down-river transitions, hollow infilling through increasing sediment accretion and root zone expansion were predominant processes driving loss of microtopography as marshes replaced TFFWs closer to the estuarine interface; hollows gained elevations to meet hummocks. While these results do not preclude the importance of healthy root zone processes to the maintenance (and formation) of hummocks, our results indicate that reductions in critical sediment supplies to offset natural shallow subsidence explain persistence and eventual loss of hummock and hollow microtopography in TFFWs.

Estuaries and Coasts↗

Annual growth patterns of baldcypress ( Taxodium distichum ) along salinity gradients

The effects of salinity on Taxodium distichum seedlings have been well documented, but few studies have examined mature trees in situ. We investigated the environmental drivers of T. distichum growth along a salinity gradient on the Waccamaw (South Carolina) and Savannah (Georgia) Rivers. On each river, T. distichum increment cores were collected from a healthy upstream site (Upper), a moderately degraded mid-reach site (Middle), and a highly degraded downstream site (Lower). Chronologies were successfully developed for Waccamaw Upper and Middle, and Savannah Middle. Correlations between standardized chronologies and environmental variables showed significant relationships between T. distichum growth and early growing season precipitation, temperature, and Palmer Drought Severity Index (PDSI). Savannah Middle chronology correlated most strongly with August river salinity levels. Both lower sites experienced suppression/release events likely in response to local anthropogenic impacts rather than regional environmental variables. The factors that affect T. distichum growth, including salinity, are strongly synergistic. As sea-level rise pushes the freshwater/saltwater interface inland, salinity becomes more limiting to T. distichum growth in tidal freshwater swamps; however, salinity impacts are exacerbated by locally imposed environmental modifications.

Georgia, South Carolina↗

Ion association in natural brines

Natural brines, both surface and subsurface, are highly associated aqueous solutions. Ion complexes in brines may be ion pairs in which the cation remains fully hydrated and the bond between the ions is essentially electrostatic, or coordination complexes in which one or more of the hydration water molecules are replaced by covalent bonds to the anion. Except for Cl − , the major simple ions in natural brines form ion pairs; trace and minor metals in brines form mainly coordination complexes. Limitations of the Debye-Hückel relations for activity coefficients and lack of data on definition and stability of all associated species in concentrated solutions tend to produce underestimates of the degree of ion association, except where the brines contain a very high proportion of Cl − . Data and calculations on closed basin brines of highly varied composition have been coupled with electrode measurements of single-ion activities in an attempt to quantify the degree of ion association. Such data emphasize the role of magnesium complexes. Trace metal contents of closed basin brines are related to complexes formed with major anions. Alkaline sulfo- or chlorocarbonate brines (western Great Basin) carry significant trace metal contents apparently as hydroxides or hydroxy polyions. Neutral high chloride brines (Bonneville Basin) are generally deficient in trace metals. With a knowledge of the thermodynamic properties of a natural water, many possible reactions with other phases (solids, gases, other liquids) may be predicted. A knowledge of these reactions is particularly important in the study of natural brines which may be saturated with many solid phases (silicates, carbonates, sulfates, etc.), which may have a high pH and bring about dissolution of other phases (silica, amphoteric hydroxides, CO 2 , etc.), and which because of their high density may form relatively stable interfaces with dilute waters.

Chemical Geology↗

Origin of concretionary Mn-Fe-oxides in stream sediments of Maine, U.S.A.

Studies of stream and sediment-pore waters largely explain the genesis of concretionary Mn-Fe-oxides in Maine. Waters of two small streams near Jackman, Maine, were studied in terms of pH, Eh, dissolved oxygen, dissolved organic carbon, dissolved Mn, total dissolved Fe, and ferrous and ferric Fe. Pyrite Creek has profuse concretions and coatings of Mn-Fe-oxides, whereas West Pyrite Creek has only sparse Mn-Fe-oxide stains. Pyrite Creek drains boggy terrain and West Pyrite Creek drains well-drained terrain. In West Pyrite Creek, stream and subjacent pore waters have chemical characteristics that do not differ greatly. However, dissolved Mn, ferrous Fe, dissolved oxygen, and in situ Eh measurements show that a steep Eh gradient exists between stream and subjacent pore waters of Pyrite Creek. The steep Eh gradient is manifested by the common zonation of coatings and stains on rocks in stream sediment. The bottom zone has no deposition of oxides, the middle zone is red and consists mostly of Fe-oxides, and the upper zone is black or dark-brown and consists of Mn-oxides with varying amounts of Fe-oxides. The zonation agrees with theoretical predictions of oxide stability as one moves from a reducing to an oxidizing environment. At locations where concretionary Mn-Fe-oxides form, pore waters are depleted of oxygen because of abundant decaying organic material in the stream sediment. The pore waters are charged with dissolved Mn and Fe because mechanically deposited Mn-Fe-oxides are remobilized due to the low-Eh conditions. Groundwaters also contribute dissolved Mn and Fe. Stream waters, on the other hand, are oxygenated and the high-Eh conditions result in low concentrations of dissolved Mn and Fe in stream waters because of the insolubility of Mn-Fe-oxides in high-Eh environments. Therefore, concretionary Mn-Fe-oxides form at the interface between pore and stream waters because Mn- and Fe-rich pore waters, which are undersaturated with respect to Mn-Fe-oxides, mix with oxygen-rich stream waters, which are saturated with respect to Mn-Fe-oxides. ?? 1983.

Chemical Geology↗

Chemical fluxes and origin of a manganese carbonate-oxide-silicate deposit in bedded chert

Lens-like rhodochrosite-rich bodies within interbedded chert and shale are associated with basalt and/or graywacke in ophiolitic and orogenic zones. The Buckeye manganese mine in the Franciscan Complex of the California Coast Ranges is associated with metagraywacke. Despite blueschist-facies metamorphism, this deposit preserves the compositions and some textural features of its sedimentary protoliths. For this reason, it is a suitable deposit with which to compare more intensely altered deposits, or deposits originating in different paleoenvironments. Six Mn-rich and three Mn-poor minerals form monomineralic layers and mixtures: rhodochrosite, gageite, Mn-oxides (hausmannite, braunite), divalent Mn-silicates (caryopilite, taneyamalite), chlorite, quartz (metachert) and aegirine-augite. The Mn-rich protoliths have high Mn/Fe combined with relatively low concentrations of Ca, Al, Ti, Co, Ni, Cu, Th and REE. REE patterns of various protoliths are distinct. Rhodochrosite and gageite layers are depleted (seawater ?? 5 ?? 104) and flat, whereas patterns of metachert and the Mn-silicate-rich layers mimic the patterns of metashale and metagraywacke (seawater ?? 106). Hausmannite layers have flat patterns (seawater ?? 7 ?? 104) whereas braunite-rich layers are more enriched (seawater ?? 2 ?? 105) and show a distinct positive Ce anomaly. Factor analysis reveals components and fluxes attributed to sub-seafloor fluids (Ni, As, Zn, Sb, W, Mn), seawater (Mg, Au, V, Mo), detritus and veins (Ca, Ba, Sr). Silica is negatively correlated with the sub-seafloor factor. The observed variances indicate that water from the sediment column mixed with seawater, that deposition occurred near the sediment-seawater interface before mixtures of subsurface fluid and seawater homogenized, and that the system was not entirely closed during metamorphism. The variations in REE enrichment can be related to kinetics of deposition: rhodochrosite and gageite were precipitated most rapidly, and therefore were the protoliths that most effectively diluted the REE-rich background resulting from fine clastic material (derived from distal turbidites). The variation of the Ce anomaly and U/Th among diverse lithologies and the differences in Mn oxidation states are consistent with progressive dilution of reduced subsurface fluids with oxidized seawater. By this scheme, rhodochrosite, gageite and hausmannite were deposited from the most reduced fluids, braunite from intermediate mixtures, and Mn-silicates from the sub-seafloor fluids most diluted with fresh seawater. Comparison of the Buckeye with other lens-like and sheet-like deposits having high Mn/Fe and containing Mn3+ and/or Mn2+ suggests that each had three essential fluxes: a sub-seafloor source of Mn, a local source of very soluble silica and a source of relatively fresh, oxygenated water. Additional fluxes, such as clastics, appear to be more characteristic of the paleoenvironment than the three essential fluxes. ?? 1992.

Chemical Geology↗

Electrolytic oxidation of anthracite

An anthracite slurry can be oxidized only with difficulty by electrolytic methods in which aqueous electrolytes are used if the slurry is confined to the region of the anode by a porous pot or diaphragm. However, it can be easily oxidized if the anthracite itself is used as the anode. No porous pot or diaphragm is needed. Oxidative consumption of the coal to alkali-soluble compounds is found to proceed preferentially at the edges of the aromatic planes. An oxidation model is proposed in which the chief oxidants are molecular and radical species formed by the electrolytic decomposition of water at the coal surface-electrolyte interface. The oxidation reactions proposed account for the opening of the aromatic rings and the subsequent formation of carboxylic acids. The model also explains the observed anisotropic oxidation and the need for the porous pot or diaphragm used in previous studies of the oxidation of coal slurries.

Fuel↗