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Hepeviruses of fish

Originally reported from California, the cutthroat trout virus (CTV) has now been isolated from eight species of salmonids in North America. Early work focused on the replication and physical characteristics of the small, round virus, but not until 20 years later was it determined to be most closely related to viruses causing hepatitis E in humans or infecting avian and mammalian hosts. The genome of CTV consists of 7269 nucleotides of positive-sense, single-stranded RNA with a genome organization similar to other members of the family Hepeviridae , although the amino acid sequence identity appears low enough to support creation of a novel genus. While CTV has not been associated with acute disease in fish, the virus was able to form persistently infected cell cultures that may aid research in treatment of hepatitis E-like viruses affecting humans or other animals. Interestingly, trout exposed to CTV were protected for about a month against subsequent exposure to Infectious hematopoietic necrosis virus . Replicating agents suspected to be CTV can be confirmed by polymerase chain reaction (PCR) and sequencing.

Book chapter↗

Hepeviruses of aquatic organisms

Originally reported in California, the cutthroat trout virus (CTV) has now been isolated from nine species of salmonids in North America. Early work focused on the replication and physical characteristics of the virus, but 20 years later was determined to be most closely related to the hepatitis E virus. The small genome is positive-sense, single-stranded RNA similar to other members of the family Hepeviridae , which now contains its own genus Piscihepevirus with two distinct genotypes, CTV-1 and CTV-2. While CTV has not been associated with acute disease in fish, the virus could form persistently infected cell cultures that may aid research in treating hepatitis E-like viruses affecting humans or other animals. Interestingly, trout exposed to CTV were protected for about a month against subsequent exposure to the infectious hematopoietic necrosis virus. Replicating agents suspected to be CTV can be confirmed by polymerase chain reaction (PCR), quantitative PCR, and sequencing. Other unclassified hepeviruses detected in fish using viral metagenomics include Wenling fish hepevirus, Wenling moray eel hepevirus, Murray–Darling carp hepevirus, and eastern mosquitofish hepevirus. The family Hepeviridae has been placed in the order Hepevirales together with the family Matonaviridae (rubella virus), with member viruses having amino acid homology in the helicase and replicase regions of the nonstructural proteins. In addition, using next-generation sequencing, a hepe-like sequence was characterized in diseased giant freshwater prawn Macrobrachium rosenbergii and named Crustacea hepe-like virus 1. Thus the family Hepeviridae continues to expand among aquatic animal hosts.

Book chapter↗

Paramyxoviruses of fish

The first fish paramyxovirus was isolated from normal adult Chinook salmon returning to a coastal hatchery in Oregon in the fall of 1982. Subsequently, the virus was isolated from other stocks of adult Chinook salmon and one stock of adult coho salmon in California, Oregon, Washington, and Alaska, leading to its designation as the Pacific salmon paramyxovirus (PsaPV). The slow-growing virus can be isolated from tissues and ovarian fluids of healthy adult fish returning to spawn and apparently causes no clinical signs of disease or mortality. In 1995 a different and widely disseminated paramyxovirus was isolated from farmed Atlantic salmon in Norway and was designated as Atlantic salmon paramyxovirus (AsaPV). Although this virus caused no disease or mortality when injected into juvenile Atlantic salmon, AsaPV has been associated with proliferative gill inflammation in sea-reared yearling fish; however, additional infectious agents may be involved in the etiology of the condition. Sequence analysis of PsaPV and AsaPV isolates using the polymerase gene established their placement in the family Paramyxoviridae and has shown the two viruses to be closely related but sufficiently different from each other and from other known paramyxoviruses to represent a new genus within the family. The viruses can be diagnosed by isolation in cell culture with final confirmation by molecular methods. Other paramyxovirus-like agents have been observed or isolated from rainbow trout in Germany, from seabream in Japan associated with epithelial necrosis, from turbot in Spain associated with erythrocytic inclusion bodies and buccal/opercular hemorrhaging and from koi and common carp associated with gill necrosis in the European Union.

Book chapter↗

Planktic foraminifera

Planktic foraminifera are single-celled marine organisms that secrete calcium carbonate tests. They live in the ocean's photic zone, and when they die, their tests, each about the size of a grain of sand, collect on the ocean floor. The geographic distribution of planktic foraminifera is mostly governed by the temperature and salinity of the ocean surface, and species assemblages are generally arranged in latitudinal bands from polar to tropical, with more species occupying warmer waters. Their ubiquity in the world's oceans since the Cretaceous Period makes them ideal biostratigraphic markers, and their sensitivity to environmental changes makes them excellent proxies of past ecological, oceanographic and climatic history.

Book chapter↗

Aeromicrobiology/air quality

The most prevalent microorganisms, viruses, bacteria, and fungi, are introduced into the atmosphere from many anthropogenic sources such as agricultural, industrial and urban activities, termed microbial air pollution (MAP), and natural sources. These include soil, vegetation, and ocean surfaces that have been disturbed by atmospheric turbulence. The airborne concentrations range from nil to great numbers and change as functions of time of day, season, location, and upwind sources. While airborne, they may settle out immediately or be transported great distances. Further, most viable airborne cells can be rendered nonviable due to temperature effects, dehydration or rehydration, UV radiation, and/or air pollution effects. Mathematical microbial survival models that simulate these effects have been developed.

Book chapter↗

Crust and lithospheric structure – Global crustal structure

The Earth’s crust has played an important role in all aspects of this planet’s evolution. This chapter presents a review of our current understanding of the physical properties of the crust on a global basis. This understanding comes from extensive seismic measurements using many techniques, as well as nonseismic geophysics, including gravity, magnetic, geoelectric, and heat flow measurements. Seismic measurements include those that employ active (man-made) sources and those that use passive (naturally occurring) sources. Deep seismic reflection profiles provide a seismic image of the crust in twodimensions with a high (50–100m) resolution. Local earthquake tomography can provide three-dimensional (3-D) seismic images at moderate (500–1000m) resolution and higher, depending on the number and spacing of seismographs. Nonseismic methods provide estimates of crustal density, magnetic properties, conductivity and geotherms (temperature vs depth). The crust in deep ocean basins is 6–7km thick and has a relatively uniform seismic velocity structure, but there are numerous oceanic regions with anomalous crustal structure, including mid-ocean ridges, trenches, volcanic islands, and oceanic plateaux. Ocean–continent passive margins are also highly variable in structure, and may be classified as volcanic versus nonvolcanic margins. Continental crust ranges in thickness from 16 to 80km, and has a highly variable seismic velocity and density structure. The proportions of continental crust, by area, are 69% shield and platform (cratons), 15% old and young orogens, 9% extended (stretched) crust, 6 % magmatic arc, and 1% rifts. The weighted mean continental crustal thickness and average crustal velocity are 41km (SD 6.2km) and 6.45kms−1 (SD 0.21kms−1), respectively. A global geographic distribution of seismic data has made it possible to create global crustal models with cell sizes as small as 2°×2°. These models provide a complete description of seismic velocities and density within the crust and uppermost mantle, including, where present, ice, water, and sedimentary layers and the crystalline crust (parameterized in three layers, upper, middle and lower crust), and sub-Moho properties. The crust is the most intensely studied region of the Earth’s interior and consequently is the best understood in terms of its structure, composition, and evolution. © 2007 Elsevier B.V. All rights reserved.

Book chapter↗

Role of chemotaxis in the transport of bacteria through saturated porous media

Populations of chemotactic bacteria are able to sense and respond to chemical gradients in their surroundings and direct their migration toward increasing concentrations of chemicals that they perceive to be beneficial to their survival. It has been suggested that this phenomenon may facilitate bioremediation processes by bringing bacteria into closer proximity to the chemical contaminants that they degrade. To determine the significance of chemotaxis in these processes it is necessary to quantify the magnitude of the response and compare it to other groundwater processes that affect the fate and transport of bacteria. We present a systematic approach toward quantifying the chemotactic response of bacteria in laboratory scale experiments by starting with simple, well-defined systems and gradually increasing their complexity. Swimming properties of individual cells were assessed from trajectories recorded by a tracking microscope. These properties were used to calculate motility and chemotaxis coefficients of bacterial populations in bulk aqueous media which were compared to experimental results of diffusion studies. Then effective values of motility and chemotaxis coefficients in single pores, pore networks and packed columns were analyzed. These were used to estimate the magnitude of the chemotactic response in porous media and to compare with dispersion coefficients reported in the field. This represents a compilation of many studies over a number of years. While there are certainly limitations with this approach for ultimately quantifying motility and chemotaxis in granular aquifer media, it does provide insight into what order of magnitude responses are possible and which characteristics of the bacteria and media are expected to be important.

Advances in Water Resources↗

Cutthroat trout virus as a surrogate in vitro infection model for testing inhibitors of hepatitis E virus replication

Hepatitis E virus (HEV) is one of the most important causes of acute hepatitis worldwide. Although most infections are self-limiting, mortality is particularly high in pregnant women. Chronic infections can occur in transplant and other immune-compromised patients. Successful treatment of chronic hepatitis E has been reported with ribavirin and pegylated interferon-alpha, however severe side effects were observed. We employed the cutthroat trout virus (CTV), a non-pathogenic fish virus with remarkable similarities to HEV, as a potential surrogate for HEV and established an antiviral assay against this virus using the Chinook salmon embryo (CHSE-214) cell line. Ribavirin and the respective trout interferon were found to efficiently inhibit CTV replication. Other known broad-spectrum inhibitors of RNA virus replication such as the nucleoside analog 2′-C-methylcytidine resulted only in a moderate antiviral activity. In its natural fish host, CTV levels largely fluctuate during the reproductive cycle with the virus detected mainly during spawning. We wondered whether this aspect of CTV infection may serve as a surrogate model for the peculiar pathogenesis of HEV in pregnant women. To that end the effect of three sex steroids on in vitro CTV replication was evaluated. Whereas progesterone resulted in marked inhibition of virus replication, testosterone and 17β-estradiol stimulated viral growth. Our data thus indicate that CTV may serve as a surrogate model for HEV, both for antiviral experiments and studies on the replication biology of the Hepeviridae.

Antiviral Research↗

A survey of the occurrence of Bacillus anthracis in North American soils over two long-range transects and within post-Katrina New Orleans

Soil samples were collected along a north-south transect extending from Manitoba, Canada, to the US-Mexico border near El Paso, Texas in 2004 (104 samples), a group of sites within New Orleans, Louisiana following Hurricane Katrina in 2005 (19 samples), and a Gulf Coast transect extending from Sulphur, Louisiana, to DeFuniak Springs, Florida, in 2007 (38 samples). Samples were collected from the top 40 cm of soil and were screened for the presence of total Bacillus species and Bacillus anthracis (anthrax), specifically using multiplex-polymerase chain reaction (PCR). Using an assay with a sensitivity of ???170 equivalent colony-forming units (CFU) g -1 field moist soil, the prevalence rate of Bacillus sp./B. anthracis in the north-south transect and the 2005 New Orleans post-Katrina sample set were 20/5% and 26/26%, respectively. Prevalence in the 2007 Gulf Coast sample set using an assay with a sensitivity of ???4 CFU g -1 of soil was 63/0%. Individual transect-set data indicate a positive relation between occurrences of species and soil moisture or soil constituents (i.e., Zn and Cu content). The 2005 New Orleans post-Katrina data indicated that B. anthracis is readily detectable in Gulf Coast soils following flood events. The data also indicated that occurrence, as it relates to soil chemistry, may be confounded by flood-induced dissemination of germinated cells and the mixing of soil constituents for short temporal periods following an event.

Applied Geochemistry↗

Size and elemental distributions of nano- to micro-particulates in the geochemically-stratified Great Salt Lake

The characterization of trace elements in terms of their apportionment among dissolved, macromolecular, nano- and micro-particulate phases in the water column of the Great Salt Lake carries implications for the potential entry of toxins into the food web of the lake. Samples from the anoxic deep and oxic shallow brine layers of the lake were fractionated using asymmetric flow field-flow fractionation (AF4). The associated trace elements were measured via online collision cell inductively-coupled plasma mass spectrometry (CC-ICP-MS). Results showed that of the total (dissolved + particulate) trace element mass, the percent associated with particulates varied from negligible (e.g. Sb), to greater than 50% (e.g. Al, Fe, Pb). Elements such as Cu, Zn, Mn, Co, Au, Hg, and U were associated with nanoparticles, as well as being present as dissolved species. Particulate-associated trace elements were predominantly associated with particulates larger than 450 nm in size. Among the smaller nanoparticulates (<450 nm), some trace elements (Ni, Zn, Au and Pb) showed higher percent mass (associated with nanoparticles) in the 0.9-7.5 nm size range relative to the 10-250 nm size range. The apparent nanoparticle size distributions were similar between the two brine layers; whereas, important differences in elemental associations to nanoparticles were discerned between the two layers. Elements such as Zn, Cu, Pb and Mo showed increasing signal intensities from oxic shallow to anoxic deep brine, suggesting the formation of sulfide nanoparticles, although this may also reflect association with dissolved organic matter. Aluminum and Fe showed greatly increased concentration with depth and equivalent size distributions that differed from those of Zn, Cu, Pb and Mo. Other elements (e.g. Mn, Ni, and Co) showed no significant change in signal intensity with depth. Arsenic was associated with <2 nm nanoparticles, and showed no increase in concentration with depth, possibly indicating dissolved arsenite. Mercury was associated with <2 nm nanoparticles, and showed greatly increased concentration with depth, possibly indicating association with dissolved organic matter. ?? 2009 Elsevier Ltd.

Applied Geochemistry↗

Widespread occurrence of intersex in black basses (Micropterus spp.) from U.S. rivers, 1995-2004

Intersex occurrence in freshwater fishes was evaluated for nine river basins in the United States. Testicular oocytes (predominantly male testes containing female germ cells) were the most pervasive form of intersex observed, even though similar numbers of male (n = 1477) and female (n = 1633) fish were examined. Intersex was found in 3% of the fish collected. The intersex condition was observed in four of the 16 species examined (25%) and in fish from 34 of 111 sites (31%). Intersex was not found in multiple species from the same site but was most prevalent in largemouth bass (Micropterus salmoides; 18% of males) and smallmouth bass (M. dolomieu; 33% of males). The percentage of intersex fish per site was 8-91% for largemouth bass and 14-73% for smallmouth bass. The incidence of intersex was greatest in the southeastern United States, with intersex largemouth bass present at all sites in the Apalachicola, Savannah, and Pee Dee River Basins. Total mercury, trans-nonachlor, p,p???-DDE, p,p???-DDD, and total PCBs were the most commonly detected chemical contaminants at all sites, regardless of whether intersex was observed. Although the genotype of the intersex fish was not determined, the microscopic appearance of the gonads, the presence of mature sperm, and the concentrations of sex steroid hormones and vitellogenin indicate the intersex bass were males. Few reproductive endpoints differed significantly among male and intersex bass; plasma vitellogenin concentration in males was not a good indicator of intersex presence. Hierarchical linkages of the intersex condition to reproductive function will require a more quantitative measure of intersex (e.g. severity index) rather than presence or absence of the condition. The baseline incidence of intersex gonadal tissue in black basses and other freshwater fishes is unknown, but intersex prevalence may be related to collection season, age, and endocrine active compounds in the environment. Intersex was not found in largemouth bass older than five years and was most common in 1-3-year-old male largemouth bass. The cause(s) of intersex in these species is also unknown, and it remains to be determined whether the intersex we observed in largemouth and smallmouth bass developed during sex differentiation in early life stages, during exposure to environmental factors during adult life stages, or both.

Aquatic Toxicology↗

Changes in reproductive biomarkers in an endangered fish species (bonytail chub, Gila elegans) exposed to low levels of organic wastewater compounds in a controlled experiment

In arid regions of the southwestern United States, municipal wastewater treatment plants commonly discharge treated effluent directly into streams that would otherwise be dry most of the year. A better understanding is needed of how effluent-dependent waters (EDWs) differ from more natural aquatic ecosystems and the ecological effect of low levels of environmentally persistent organic wastewater compounds (OWCs) with distance from the pollutant source. In a controlled experiment, we found 26 compounds common to municipal effluent in treatment raceways all at concentrations <1.0 μg/L. Male bonytail chub (Gila elegans) in tanks containing municipal effluent had significantly lower levels of 11-ketotestosterone (p = 0.021) yet higher levels of 17β-estradiol (p = 0.002) and vitellogenin (p = 0.036) compared to control male fish. Female bonytail chub in treatment tanks had significantly lower concentrations of 17β-estradiol than control females (p = 0.001). The normally inverse relationship between primary male and female sex hormones, expected in un-impaired fish, was greatly decreased in treatment (r = 0.00) versus control (r = −0.66) female fish. We found a similar, but not as significant, trend between treatment (r = −0.45) and control (r = −0.82) male fish. Measures of fish condition showed no significant differences between male or female fish housed in effluent or clean water. Inter-sex condition did not occur and testicular and ovarian cells appeared normal for the respective developmental stage and we observed no morphological alteration in fish. The population-level impacts of these findings are uncertain. Studies examining the long-term, generational and behavioral effects to aquatic organisms chronically exposed to low levels of OWC mixtures are needed.

Aquatic Toxicology↗

Atrazine reduces reproduction in Japanese medaka (Oryzias latipes)

Atrazine is an effective broadleaf herbicide and the second most heavily used herbicide in the United States. Effects along the hypothalamus–pituitary–gonad axis in a number of vertebrate taxa have been demonstrated. Seasonally elevated concentrations of atrazine in surface waters may adversely affect fishes, but only a few studies have examined reproductive effects of this chemical. The present study was designed to evaluate a population endpoint (egg production) in conjunction with histological (reproductive stage, gonad pathology) and biochemical (aromatase activity, sex hormone production) phenotypes associated with atrazine exposure in Japanese medaka. Adult virgin breeding groups of one male and four females were exposed to nominal concentrations of 0, 0.5, 5.0, and 50 μg/L (0, 2.3, 23.2, 231 nM) of atrazine in a flow-through diluter for 14 or 38 days. Total egg production was lower (36–42%) in all atrazine-exposed groups as compared to the controls. The decreases in cumulative egg production of atrazine-treated fish were significant by exposure day 24. Reductions in total egg production in atrazine treatment groups were most attributable to a reduced number of eggs ovulated by females in atrazine-treated tanks. Additionally, males exposed to atrazine had a greater number of abnormal germ cells. There was no effect of atrazine on gonadosomatic index, aromatase protein, or whole body 17 β-estradiol or testosterone. Our results suggest that atrazine reduces egg production through alteration of final maturation of oocytes. The reduced egg production observed in this study was very similar to our previously reported results for fathead minnow. This study provides further information with which to evaluate atrazine's risk to fish populations.

Aquatic Toxicology↗

Sublethal red tide toxin exposure in free-ranging manatees (Trichechus manatus) affects the immune system through reduced lymphocyte proliferation responses, inflammation, and oxidative stress

The health of many Florida manatees (Trichechus manatus latirostris) is adversely affected by exposure to blooms of the toxic dinoflagellate, Karenia brevis. K. brevis blooms are common in manatee habitats of Florida's southwestern coast and produce a group of cyclic polyether toxins collectively referred to as red tide toxins, or brevetoxins. Although a large number of manatees exposed to significant levels of red tide toxins die, several manatees are rescued from sublethal exposure and are successfully treated and returned to the wild. Sublethal brevetoxin exposure may potentially impact the manatee immune system. Lymphocyte proliferative responses and a suite of immune function parameters in the plasma were used to evaluate effects of brevetoxin exposure on health of manatees rescued from natural exposure to red tide toxins in their habitat. Blood samples were collected from rescued manatees at Lowry Park Zoo in Tampa, FL and from healthy, unexposed manatees in Crystal River, FL. Peripheral blood leukocytes (PBL) isolated from whole blood were stimulated with T-cell mitogens, ConA and PHA. A suite of plasma parameters, including plasma protein electrophoresis profiles, lysozyme activity, superoxide dismutase (SOD) activity, and reactive oxygen/nitrogen (ROS/RNS) species, was also used to assess manatee health. Significant decreases (p<0.05) in lymphocyte proliferation were observed in ConA and PHA stimulated lymphocytes from rescued animals compared to non-exposed animals. Significant correlations were observed between oxidative stress markers (SOD, ROS/RNS) and plasma brevetoxin concentrations. Sublethal exposure to brevetoxins in the wild impacts some immune function components, and thus, overall health, in the Florida manatee.

Florida↗

Validating the performance of occupancy models for estimating habitat use and predicting the distribution of highly-mobile species: A case study using the American black bear

Occupancy models have become a valuable tool for estimating wildlife-habitat relationships and for predicting species distributions. Highly-mobile species often violate the assumption that sampling units are geographically closed shifting the probability of occupancy to be interpreted as the probability of use. We used occupancy models, in conjunction with noninvasive sampling, to estimate habitat use and predict the distribution of a highly-mobile carnivore, the American black bear ( Ursus americanus ) in New Mexico, USA. The top model indicated that black bears use areas with higher primary productivity and fewer roads. The predictive performance of such models is rarely validated with independent data, so we validated our model predictions with 2-independent datasets. We first assessed the correlation between predicted and observed habitat use for 28 telemetry-collared bears in the Jemez Mountains. Predicted habitat use was positively correlated with observed use for all 3 years (2012: ρ = 0.81; 2013: ρ = 0.87; 2014: ρ = 0.90). We then predicted the probability of use within a cell where a bear mortality was documented using 2043 mortality locations from sport harvest, depredation, and vehicle collisions. The probability of habitat use at a mortality location was also positively correlated with observed use by the species (2012: ρ = 0.74; 2013: ρ = 0.89; 2014: ρ = 0.93). Our validation procedure supports the notion that occupancy models can be an effective tool for estimating habitat use and predicting the distribution of highly-mobile species when the assumption of geographic closure has been violated. Our findings may be of interest to studies that are estimating habitat use for highly-mobile species that are secretive or rare, difficult to capture, or expensive to monitor with other more intensive methods.

New Mexico↗

EverVIEW: a visualization platform for hydrologic and Earth science gridded data

The EverVIEW Data Viewer is a cross-platform desktop application that combines and builds upon multiple open source libraries to help users to explore spatially-explicit gridded data stored in Network Common Data Form (NetCDF). Datasets are displayed across multiple side-by-side geographic or tabular displays, showing colorized overlays on an Earth globe or grid cell values, respectively. Time-series datasets can be animated to see how water surface elevation changes through time or how habitat suitability for a particular species might change over time under a given scenario. Initially targeted toward Florida's Everglades restoration planning, EverVIEW has been flexible enough to address the varied needs of large-scale planning beyond Florida, and is currently being used in biological planning efforts nationally and internationally.

Computers & Geosciences↗

Supergene destruction of a hydrothermal replacement alunite deposit at Big Rock Candy Mountain, Utah: Mineralogy, spectroscopic remote sensing, stable-isotope, and argon-age evidences

Big Rock Candy Mountain is a prominent center of variegated altered volcanic rocks in west-central Utah. It consists of the eroded remnants of a hypogene alunite deposit that, at ∼21 Ma, replaced intermediate-composition lava flows. The alunite formed in steam-heated conditions above the upwelling limb of a convection cell that was one of at least six spaced at 3- to 4-km intervals around the margin of a monzonite stock. Big Rock Candy Mountain is horizontally zoned outward from an alunite core to respective kaolinite, dickite, and propylite envelopes. The altered rocks are also vertically zoned from a lower pyrite–propylite assemblage upward through assemblages successively dominated by hypogene alunite, jarosite, and hematite, to a flooded silica cap. This hydrothermal assemblage is undergoing natural destruction in a steep canyon downcut by the Sevier River in Marysvale Canyon. Integrated geological, mineralogical, spectroscopic remote sensing using AVIRIS data, Ar radiometric, and stable isotopic studies trace the hypogene origin and supergene destruction of the deposit and permit distinction of primary (hydrothermal) and secondary (weathering) processes. This destruction has led to the formation of widespread supergene gypsum in cross-cutting fractures and as surficial crusts, and to natrojarosite, that gives the mountain its buff coloration along ridges facing the canyon. A small spring, Lemonade Spring, with a pH of 2.6 and containing Ca, Mg, Si, Al, Fe, Mn, Cl, and SO 4 , also occurs near the bottom of the canyon. The 40 Ar/ 39 Ar age (21.32±0.07 Ma) of the alunite is similar to that for other replacement alunites at Marysvale. However, the age spectrum contains evidence of a 6.6-Ma thermal event that can be related to the tectonic activity responsible for the uplift that led to the downcutting of Big Rock Candy Mountain by the Sevier River. This ∼6.6 Ma event also is present in the age spectrum of supergene natrojarosite forming today, and probably dates the beginning of supergene alteration at Big Rock Candy Mountain. The δ 34 S value (11.9‰) of alunite is similar to those for replacement alunite from other deposits in the Marysvale volcanic field. The δ 34 S values of natrojarosite (0.7‰ to −1.2‰) are similar to those for aqueous sulfate in Lemonade Spring, but are larger than those in pyrite (0.4‰ to −4.7‰). The δ 34 S and δ 18 O SO 4 values of gypsum show an excellent correlation, with values ranging from 15.2‰ to −5.2‰ and 7‰ to −8.2‰, respectively. The stable-isotope data indicate that the aqueous sulfate for gypsum is a mixture derived from the dissolution of hypogene gypsum and alunite, and from the supergene oxidation of pyrite. The aqueous sulfate for the natrojarosite, however, is derived largely from the supergene oxidation of pyrite, with a minor contribution from the dissolution of alunite and gypsum. The exceptional detailed spectral mapping capabilities of AVIRIS led to the recognition of a small amount of jarosite that is probably the top of the steam-heated system that produced the primary hypogene alteration at Big Rock Candy Mountain.

Utah↗

On the formation and structure of rare-earth element complexes in aqueous solutions under hydrothermal conditions with new data on gadolinium aqua and chloro complexes

Synchrotron X-ray spectroscopy experiments were made on the Gd(III) aqua and chloro complexes in low pH aqueous solutions at temperatures ranging from 25 to 500????C and at pressures up to 480??MPa using a hydrothermal diamond anvil cell. Analysis of fluorescence Gd L3-edge X-ray absorption fine structure (XAFS) spectra measured from a 0.006m Gd/0.16m HNO3 aqueous solution at temperatures up to 500????C and at pressures up to 260??MPa shows that the Gd-O distance of the Gd3+ aqua ion decreases steadily at a rate of ??? 0.007??A??/100????C whereas the number of coordinated H2O molecules decreases from 9.0 ?? 0.5 to 7.0 ?? 0.4. The loss of water molecules in the Gd3+ aqua ion inner hydration shell over this temperature range (a 22% reduction) is smaller than exhibited by the Yb3+ aqua ion (42% reduction) indicating that the former is significantly more stable than the later. We conjecture that the anomalous enrichment of Gd reported from measurement of REE concentrations in ocean waters may be attributed to the enhanced stability of the Gd3+ aqua ion relative to other REEs. Gd L3-edge XAFS measurements of 0.006m and 0.1m GdCl3 aqueous solutions at temperatures up to 500????C and pressures up to 480??MPa reveal that the onset of significant Gd3+-Cl- association occurs around 300????C. Partially-hydrated stepwise inner-sphere complexes most likely of the type Gd(H2O)??-nCln+3-n occur in the chloride solutions at higher temperatures, where ?? ??? 8 at 300????C decreasing slightly to an intermediate value between 7 and 8 upon approaching 500????C. This is the first direct evidence for the occurrence of partially-hydrated REE Gd (this study) and Yb [Mayanovic, R.A., Jayanetti, S., Anderson, A.J., Bassett, W.A., Chou, I-M., 2002a. The structure of Yb3+ aquo ion and chloro complexes in aqueous solutions at up to 500 ??C and 270 MPa. J. Phys. Chem. A 106, 6591-6599.] chloro complexes in hydrothermal solutions. The number of chlorides (n) of the partially-hydrated Gd(III) chloro complexes increases steadily with temperature from 0.4 ?? 0.2 to 1.7 ?? 0.3 in the 0.006m chloride solution and from 0.9 ?? 0.7 to 1.8 ?? 0.7 in the 0.1m GdCl3 aqueous solution in the 300-500????C range. Conversely, the number of H2O ligands of Gd(H2O)??-nCln+3-n complexes decreases steadily from 8.9 ?? 0.4 to 5.8 ?? 0.7 in the 0.006m GdCl3 aqueous solution and from 9.0 ?? 0.5 to 5.3 ?? 1.0 in the 0.1m GdCl3 aqueous solution at temperatures from 25 to 500????C. Analysis of our results shows that the chloride ions partially displace the inner-shell water molecules during Gd(III) complex formation under hydrothermal conditions. The Gd-OH2 bond of the partially-hydrated Gd(III) chloro complexes exhibits slightly smaller rates of length contraction (??? 0.005??A??/100????C) for both solutions. The structural aspects of chloride speciation of Gd(III) as measured from this study and of Yb(III) as measured from our previous experiments are consistent with the solubility of these and other REE in deep-sea hydrothermal fluids. ?? 2006 Elsevier B.V. All rights reserved.

Chemical Geology↗