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USGS2008

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↗

USGS2010

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↗

USGS2016

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↗

USGS2014

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↗

USGS2016

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—defined as the tidal volume divided by the volume of burrows— 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↗

USGS2017

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↗

USGS2023

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↗

USGS2015

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↗

USGS1969

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↗

USGS1983

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↗

USGS1992

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↗

USGS1981

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↗

USGS1977

Ore transport and deposition in the Red Sea geothermal system: a geochemical model

Thermodynamic calculation of distribution of dissolved aqueous species in the Red Sea geothermal brine provides a model of ore transport and deposition in good agreement with observed accumulations of base metal sulfides, anhydrite, and barite. The Red Sea brine is recirculated seawater that acquires high salinity by low-temperature interaction with Miocene evaporites and is subsequently heated to temperatures in excess of 200°C by interaction with recent rift zone intrusive rocks. At temperatures up to 250°C, NaSO − 4 and MgSO 0 4 are the dominant sulfur-bearing species. H 2 S forms by inorganic sulfate reduction at the higher temperatures but is maintained at a uniform concentration of about 2 ppm by the strength of the sulfate complexes. Chloride complexes solubilize metals at the higher temperatures, and thus sulfide and metals are carried together into the Atlantis II Deep. Below 150°C, the brine becomes supersaturated with respect to chalcopyrite, sphalerite, galena, and iron monosulfide due to chloride-complex dissociation. Sulfide precipitation rates, based on the rate of brine influx, are in good agreement with measured sedimentation rates. Anhydrite precipitates as crystalline fissure infillings from high-temperature inflowing brine. Barite forms from partial oxidation of sulfides at the interface between the lower hot brine and the transitional brine layer.

Geochimica et Cosmochimica Acta↗

USGS1983

An interpretation of carbon and sulfur relationships in Black Sea sediments as indicators of environments of deposition

Syngenetic iron sulfides in sediments are formed from dissolved sulfide resulting from sulfate reduction and catabolism of organic matter by anaerobic bacteria. It has been shown that in recent marine sediments deposited below oxygenated waters there is a constant relationship between reduced sulfur and organic carbon which is generally independent of the environment of deposition. Reexamination of data from recent sediments from euxinic marine environments ( e.g. , the Black Sea) also shows a linear relationship between carbon and sulfur, but the slope is variable and the line intercepts the S axis at a value between 1 and 2 percent S. It is proposed that the positive S intercept is due to watercolumn microbial reduction of sulfate using metabolizable small organic molecules and the sulfide formed is precipitated and accumulates at the sediment-water interface. The variation in slope and intercept of the C to S plots for several cores and for different stratigraphic zones for the Black Sea can be interpreted in relation to thickness of the aqueous sulfide layer or thinness of the oxygen containing layer and to deposition rate, but also may be influenced by availability of iron, and perhaps the type of organic matter (Leventhal, 1979).

Geochimica et Cosmochimica Acta↗

USGS1991

An AEM-TEM study of weathering and diagenesis, Abert Lake, Oregon: II. Diagenetic modification of the sedimentary assemblage

This paper compares the mineralogy and chemistry of clay minerals in sediments from various depths and positions in Abert Lake and surrounding playa with those of the weathered materials entering the lake in order to reveal the nature and extent of post-depositional mineralogical modification. Analytical electron microscope (AEM) data from individual clay particles reveal that each sample is comprised of a highly inhomogeneous smectite assemblage. The thin clay flakes (commonly less than 10 nm wide) display a complete range in octahedral sheet compositions from nearly dioctahedral to nearly trioctahedral. The very abundant Mg-rich lake smectites with an estimated composition K 0.29 (Al 0.23 -Mg 2.16 Fe 0.30 )Si 3.80 Al 0.20 O 10 (OH) 2 are not formed by weathering. This confirms the importance of diagenetic Mg uptake. Lattice-fringe imaging failed to reveal distinct brucite-like or vermiculite-like layers, suggesting that interstratifications of this type are rare or absent. Siliceous coatings on clay particles (identified by silica excess in smectite analyses) seem to favor topotactic overgrowth of stevensite rather than addition of brucite-like layers to the dioctahedral nuclei. The growth of K-stevensite dilutes the Al content of the crystal, and thus the increasing diagenetic modification reduces rather than supplements its illite component. Smectite compositions within individual samples were highly variable, yet source-related characteristics such as the abundance of Fe-rich smectite were apparent. Little evidence for systematic K or Mg enrichment with depth was identified in samples from depths of down to 16 feet below the sediment-water interface. The most magnesian assemblages are associated both with weathering sources of Mg-rich smectite and playa environments subjected to repeated wetting and drying cycles. Thus, the observations suggest that clay compositions primarily reflect changes in lake levels, brine composition, and source characteristics, rather than time and depth/compaction effects. Other diagenetic reactions in the sediment include recrystallization of Na-rich silica gel and diatom fragments. Abundant, submicron-sized, untwinned, euhedral crystals of K-feldspar are interpreted to be authigenic in origin.

Geochimica et Cosmochimica Acta↗

USGS1993

Surface chemistry of ferrihydrite: Part 1. EXAFS studies of the geometry of coprecipitated and adsorbed arsenate

EXAFS spectra were collected on both the As and Fe K-edges from samples of two-line ferrihydrite with adsorbed (ADS) and coprecipitated (CPT) arsenate prepared over a range of conditions and arsenate surface coverages. Spectra also were collected for arsenate adsorbed on the surfaces of three FeOOH crystalline polymorphs, α (goethite), β (akaganeite), and γ (lepidocrocite), and as a free ion in aqueous: solution. Analyses of the As EXAFS show clear evidence for inner sphere bidentate (bridging) arsenate complexes on the ferrihydrite surface and on the surfaces of the crystalline FeOOH polymorphs. The bridging arsenate is attached to adjacent apices of edge-sharing Fe oxyhydroxyl octahedra. The arsenic-iron distance at the interface ( 3.28 ±0.01 A ̊ "> 3.28 ±0.01Å ) is close to that expected for this geometry on the FeOOH polymorph surfaces, but is slightly shorter on the ferrihydrite surfaces ( 3.25 ± 0.02 A ̊ "> 3.25 ± 0.02Å ). Mono-dentate arsenate linkages ( 3.60 ± 0.03 A ̊ "> 3.60 ± 0.03Å ) also occur on the ferrihydrite, but are not generally observed on the crystalline FeOOH polymorphs. The proportion of monodentate bonds appears largest for adsorption samples with the smallest As Fe "> AsFe molar ratio. In all cases the arsenate tetrahedral complex is relatively undistorted with As-O bonds of 1.66 ± 0.01 A ̊ "> 1.66 ± 0.01Å . Precipitation of arsenate or scorodite-like phases was not observed for any samples, all of which were prepared at a pH value of 8. The Fe EXAFS results confirm that the Fe-Fe correlations in the ferrihydrite are progressively disrupted in the CPT samples as the As Fe "> AsFe ratio is increased. Coherent crystallite size is probably no more than 10 Å in diameter and no Fe oxyhydroxyl octahedra corner-sharing linkages (as would be present in FeOOH polymorphs) are observed at the largest As Fe "> AsFe ratios. Comparison of the number and type of Fe-Fe neighbors with the topological constraints imposed by the arsenate saturation limit in the CPT samples (about 0.7 As Fe "> AsFe ) indicates ferrihydrite units consisting mainly of Fe oxyhydroxyl octahedra arranged in short dioctahedral chains with minimal interchain linking by octahedra corners. This is consistent with an enlarged surface area and a larger proportion of sites for bidentate arsenate bonding in CPT samples as compared to the ADS samples, which saturate with arsenate at lower As Fe "> AsFe ratios. The latter samples have larger crystallite sizes and a definite proportion of ferric octahedra sharing corners. The ratio of corner-sharing to edge-sharing Fe oxyhydroxyl octahedra in the ADS samples, and CPT samples with small As loadings, is very similar to what would be present in very small particles of goethite or akaganeite. The difference in the polymeric structure of ADS and CPT samples at higher As Fe "> AsFe ratios is due to strong arsenate bidentate adsorption that poisons the surface of particles of ferrihydrite precipitated in the presence of substantial arsenate, limiting their normal crystallization, and preventing further Fe-O-Fe polymerization. If the arsenate is applied after precipitation much less adsorption occurs since polymerization has already progressed. In both ADS and CPT samples, Fe-O-Fe polymerization increases with age, though at different rates for each type of sample.

Geochimica et Cosmochimica Acta↗

USGS1994

Re-Os isotopic evidence for an enriched-mantle source for the Noril'sk-type, ore-bearing intrusions, Siberia

Magmatic Cu-Ni sulfide ores and spatially associated ultramafic and mafic rocks from the Noril'sk I, Talnakh, and Kharaelakh intrusions are examined for Re-Os isotopic systematics. Neodymium and lead isotopic data also are reported for the ultramafic and mafic rocks. The Re-Os data for most samples indicate closed-system behavior since the ca. 250 Ma igneous crystallization age of the intrusions. There are small but significant differences in the initial osmium isotopic compositions of samples from the three intrusions. Ores from the Noril'sk I intrusion have γ Os values that vary from +0.4 to +8.8, but average +5.8. Ores from the Talnakh intrusion have γ Os values that range from +6.7 to +8.2, averaging +7.7. Ores from the Kharaelakh intrusion have γ Os values that range from +7.8 to +12.9, with an average value of +10.4. The osmium isotopic compositions of the ore samples from the Main Kharaelakh orebody exhibit minimal overlap with those for the Noril'sk I and Talnakh intrusions, indicating that these Kharaelakh ores were derived from a more radiogenic source of osmium than the other ores. Combined osmium and lead data for major orebodies in the three intrusions plot in three distinct fields, indicating derivation of osmium and lead from at least three isotopically distinct sources. Some of the variation in lead isotopic compositions may be the result of minor lower-crustal contamination. However, in contrast to most other isotopic and trace element data, Os-Pb variations are generally inconsistent with significant crustal contamination or interaction with the subcontinental lithosphere. Thus, the osmium and lead isotopic compositions of these intrusions probably reflect quite closely the compositions of their mantle source, and suggest that these two isotope systems were insensitive to lithospheric interaction. Ultramafic and mafic rocks have osmium and lead isotopic compositions that range only slightly beyond the compositions of the ores. These rocks also have relatively uniform ϵ Nd values that range only from −0.8 to + 1.1. This limited variation in neodymium isotopic composition may reflect the characteristics of the mantle sources of the rocks, or it may indicate that somehow similar proportions of crust contaminated the parental melts. The osmium, lead, and neodymium isotopic data for these rocks most closely resemble the mantle sources of certain ocean island basalts (OIB), such as some Hawaiian basalts. Hence, these data are consistent with derivation of primary melts from a mantle source similar to that of some types of hotspot activity. The long-term Re/Os enrichment of this and similar mantle sources, relative to chondritic upper mantle, may reflect 1. incorporation of recycled oceanic crust into the source more than 1 Ga ago, 2. derivation from a mantle plume that originated at the outer core-lower mantle interface, or 3. persistence of primordial stratification of rhenium and osmium in the mantle.

Siberia↗

USGS1994

Composition and origin of hydrothermal ironstones from central Pacific seamounts

Ironstones recovered from five Late Cretaceous seamounts in the central Pacific region probably formed during late-stage edifice-building volcanism. Ironstones are dense and compact with the appearance of brown chert. The ironstones are characterized by a goethite mineralogy with FeOOH contents up to 88%, extreme fractionation of Fe and Mn, low trace-element and rare earth element abundances, low Co Zn "> CoZn ratios, and isotopic equilibration temperatures of about 20–45 °C. These characteristics indicate that the ironstones formed from hydrothermal fluids. Ironstones probably formed below the seawater-seafloor interface, as indicated by their occurrence as a proximal hydrothermal deposit, presence of primary goethite cement, pervasive replacement of rocks by goethite, and absence of interbedded pyro-clastic beds.

Geochimica et Cosmochimica Acta↗