Robert R. Seal

Geochemical and isotopic (Nd-Pb-Sr-O) variations bearing on the genesis of volcanic rocks from Vesuvius, Italy

Abstract Alkaline volcanism produced by Monte Somma–Vesuvius volcano includes explosive plinian and subplinian activity in addition to effusive lava flows. Pumice, scoria, and lava (150 samples) exhibit major- and trace-element gradients as a function of SiO2 (58.9–47.2 wt%) and MgO (0–7.8 wt%); Mg# values are 10 with decreasing age for the Vesuvius system as a whole, yielding similar compositions in the least evolved rocks (low-silica, high-MgO, incompatible element-poor) erupted at the end of each cycle. Internal variations within individual eruptions also systematically changed generally toward a common mafic composition at the end of each cycle, thus reflecting the dominant volume in the magma chamber. At the start of a new eruptive cycle, the rocks are relatively enriched in incompatible elements; younger groups also contain higher abundances than older groups. N-MORB-normalized multielement diagrams exhibit selective enrichments of Sr, K, Rb, Th, and the light rare-earth elements; deep Nb and Ta negative anomalies commonly seen in rocks generated at orogenic margins are absent in our samples. Sr isotopic compositions are known to be variable within some of the units, in agreement with our data ( 87 Sr / 86 Sr ~0.70699 to 0.70803) and with contributions from several isotopic components. Isotopic compositions for δ 18 O (7.3 to 10.2‰), Pb for mineral separates and whole rocks ( 206 Pb / 204 Pb ~18.947 to 19.178, 207 Pb / 204 Pb ~15.617 to 15.769, 208 Pb / 204 Pb ~38.915 to 39.435), and Nd ( 143 Nd / 144 Nd ~0.51228 to 0.51251) also show variability. Oxygen isotope data show that pumices have higher δ 18 O values than cogenetic lavas, and that δ 18 O values and SiO2 are correlated. Radiogenic and stable isotope data plot within range of isotopic compositions for the Roman comagmatic province. Fractional crystallization cannot account for the radiogenic isotopic compositions of the Vesuvius magmas. We favor instead the combined effects of heterogeneous magma sources, together with isotopic exchange near the roof of the magma chamber. We suggest that metasomatized continental mantle lithosphere is the principal source of the magmas. This kind of enriched mantle was melted and reactivated in an area of continental extension (incipient rift setting) without direct reliance on contemporaneous subduction processes but possibly with input from mantle sources that resemble those that produce ocean island basalts.

Eutrophication and Carbon Sources in Chesapeake Bay Over the Last 2700 Yr: Human Impacts in Context

To compare natural variability and trends in a developed estuary with human-influenced patterns, stable isotope ratios ( 13 C and 15 N) were measured in sediments from five piston cores collected in Chesapeake Bay. Mixing of terrestrial and algal carbon sources primarily controls patterns of 13 Corg profiles, so this proxy shows changes in estuary productivity and in delivery of terrestrial carbon to the bay. Analyses of 15 N show periods when oxygen depletion allowed intense denitrification and nutrient recycling to develop in the seasonally stratified water column, in addition to recycling taking place in surficial sediments. These conditions produced 15 N-enriched (heavy) nitrogen in algal biomass, and ultimately in sediment. A pro- nounced increasing trend in 15 No f4‰ started in about A.D. 1750 to 1800 at all core sites, indicating greater eutrophication in the bay and summer oxygen depletion since that time. The timing of the change correlates with the advent of widespread land clearing and tillage in the watershed, and associated increases in erosion and sedimentation. Isotope data show that the region has experienced up to 13 wet-dry cycles in the last 2700 yr. Relative sea-level rise and basin infilling have produced a net freshening trend overprinted with cyclic climatic variability. Isotope data also constrain the relative position of the spring productivity maximum in Chesapeake Bay and distinguish local anomalies from sustained changes impacting large regions of the bay. This approach to reconstructing environmental history should be generally applicable to studies of other estuaries and coastal embayments impacted by watershed development. Published by Elsevier Ltd

Determination of melanterite-rozenite and chalcanthite-bonattite equilibria by humidity measurements at 0.1 MPa

Abstract Melanterite (FeSO4·7H2O)-rozenite (FeSO4·4H2O) and chalcanthite (CuSO4·5H2O)-bonattite (CuSO4·3H2O) equilibria were determined by humidity measurements at 0.1 MPa. Two methods were used; one is the gas-flow-cell method (between 21 and 98 °C), and the other is the humiditybuffer method (between 21 and 70 °C). The first method has a larger temperature uncertainty even though it is more efficient. With the aid of humidity buffers, which correspond to a series of saturated binary salt solutions, the second method yields reliable results as demonstrated by very tight reversals along each humidity buffer. These results are consistent with those obtained by the first method, and also with the solubility data reported in the literature. Thermodynamic analysis of these data yields values of 29.231 ± 0.025 and 22.593 ± 0.040 kJ/mol for standard Gibbs free energy of reaction at 298.15 K and 0.1 MPa for melanterite-rozenite and chalcanthite-bonattite equilibria, respectively. The methods used in this study hold great potential for unraveling the thermodynamic properties of sulfate salts involved in dehydration reactions at near ambient conditions.

Hydrogen isotope systematics of phase separation in submarine hydrothermal systems: Experimental calibration and theoretical models

Abstract Hydrogen isotope fractionation factors were measured for coexisting brines and vapors formed by phase separation of NaCl/H 2 O fluids at temperatures ranging from 399–450°C and pressures from 277–397 bars. It was found that brines are depleted in D compared to coexisting vapors at all conditions studied. The magnitude of hydrogen isotope fractionation is dependent on the relative amounts of Cl in the two phases and can be empirically correlated to pressure using the following relationship: 1000 In α (vap-brine) = 2.54(±0.83) + 2.87 (±0.69) × log (Δ P ), where α (vap-brine) is the fractionation factor and Δ P is a pressure term representing distance from the critical curve in the NaCl/H 2 O system.

Acquisition and evaluation of thermodynamic data for morenosite-retgersite equilibria at 0.1 MPa

Abstract Metal-sulfate salts in mine drainage environments commonly occur as solid solutions containing Fe, Cu, Mg, Zn, Al, Mn, Ni, Co, Cd, and other elements. Thermodynamic data for some of the endmember salts containing Fe, Cu, Zn, and Mg have been collected and evaluated previously, and the present study extends to the system containing Ni. Morenosite (NiSO4·7H2O)-retgersite (NiSO4·6H2O) equilibria were determined along five humidity buffer curves at 0.1 MPa and between 5 and 22 °C. Reversals along these humidity-buffer curves yield ln K = 17.58-6303.35/T, where K is the equilibrium constant, and T is temperature in K. The derived standard Gibbs free energy of reaction is 8.84 kJ/mol, which agrees very well with the values of 8.90, 8.83, and 8.85 kJ/mol based on the vapor pressure measurements of Schumb (1923), Bonnell and Burridge (1935), and Stout et al. (1966), respectively. This value also agrees reasonably well with the values of 8.65 and 9.56 kJ/mol calculated from the data compiled by Wagman et al. (1982) and DeKock (1982), respectively. The temperature- humidity relationships defined by this study for dehydration equilibria between morenosite and retgersite explain the more common occurrence of retgersite relative to morenosite in nature.

Mineralogy of mine waste at the Vermont Asbestos Group mine, Belvidere Mountain, Vermont

Abstract Samples from the surfaces of waste piles at the Vermont Asbestos Group mine in northern Vermont were studied to determine their mineralogy, particularly the presence and morphology of amphiboles. Analyses included powder X-ray diffraction (XRD), optical microscopy, scanning electron microscopy (SEM), electron probe microanalysis (EPMA), and Raman spectroscopy. Minerals identified by XRD were serpentine-group minerals, magnetite, chlorite, quartz, olivine, pyroxene, and brucite; locally, mica and carbonates were also present. Raman spectroscopy distinguished antigorite and chrysotile, which could not be differentiated using XRD. Long-count, short-range XRD scans of the (110) amphibole peak showed trace amounts of amphibole in most samples. Examination of amphiboles in tailings by optical microscopy, SEM, and EPMA revealed non-fibrous amphiboles compositionally classified as edenite, magnesiohornblende, magnesiokatophorite, and pargasite. No fibrous amphibole was found in the tailings, although fibrous tremolite was identified in a sample of host rock. Knowledge of the mineralogy at the site may lead to better understanding of potential implications for human health and aid in designing a remediation plan.

Stable isotope study of fluid inclusions in fluorite from Idaho: Implications for continental climates during the Eocene

Isotopic studies of fluid inclusions from meteoric water-dominated epithermal ore deposits offer a unique opportunity to study paleoclimates because the fluids can provide direct samples of ancient waters. The oxygen and hydrogen isotope compositions of meteoric waters vary because of changes in climatic variables such as mean annual temperature of precipitation, relative humidity, origin and history of air masses, and the isotope composition of the oceans. Inclusion fluids found in fluorite (CaF 2 ) are especially useful because their host is devoid of oxygen or hydrogen, thus precluding postentrapment isotope exchange. Fluorite-hosted fluid inclusions from the Eocene (51-50 Ma) epithermal deposits of the Bayhorse mining district, northeastern Idaho, have low salinities, most less than 0.6 equivalent wt% NaCl, and low to moderate homogenization temperatures (98 to 146 °C), indicating meteoric origins for the fluids. Oxygen and hydrogen isotope data on inclusion fluids are almost identical to those of modern meteoric waters in the area. The equivalence of the isotope composition of the Eocene inclusion fluids and modern meteoric waters indicates that the Eocene climatic conditions were similar to those today. This conclusion supports the climate modeling of Sloan and Barron, who suggested that the climates of continental interiors do not reflect the magnitude of warming preserved by the deep-ocean paleoclimate record during the Eocene.

Alpersite (Mg,Cu)SO4·7H2O, a new mineral of the melanterite group, and cuprian pentahydrite: Their occurrence within mine waste

Abstract Alpersite, Mg0.58Cu0.37Zn0.02Mn0.02Fe0.01SO4·7H2O, a new mineral species with direct relevance to reactions in mine waste, occurs in a mineralogically zoned assemblage in sheltered areas at the abandoned Big Mike mine in central Nevada at a relative humidity of 65% and T = 4 °C. Blue alpersite, which is isostructural with melanterite (FeSO4·7H2O), is overlain by a light blue to white layer dominated by pickeringite, alunogen, and epsomite. X-ray diffraction data (MoKα radiation) from a single crystal of alpersite were refined in P21/c, resulting in wR = 0.05 and cell dimensions α = 14.166(4), b = 6.534(2), c = 10.838(3) Å, β = 105.922(6)°, Z = 4. Site-occupancy refinement, constrained to be consistent with the compositional data, showed Mg to occupy the M1 site and Cu the M2 site. The octahedral distortion of M2 is consistent with 72% Cu occupancy when compared with the site-distortion data of substituted melanterite. Cuprian pentahydrite, with the formula (Mg0.49Cu0.41Mn0.08Zn0.02)SO4·5H2O, was collected from an efflorescent rim on a depression that had held water in a large waste-rock area near Miami, Arizona. After dissolution of the efflorescence in de-ionized water, and evaporation of the supernatant liquid, alpersite precipitated and quickly dehydrated to cuprian pentahydrite. These observations are consistent with previous experimental studies of the system MgSO4-CuSO4-H2O. It is suspected that alpersite and cuprian pentahydrite are widespread in mine wastes that contain Cu-bearing sulfides, but in which solubilized Fe2+ is not available for melanterite crystallization because of oxidation to Fe3+ in surface waters of near-neutral pH. Alpersite has likely been overlooked in the past because of the close similarity of its physical properties to those of melanterite and chalcanthite. Alpersite is named after Charles N. Alpers, geochemist with the United States Geological Survey, who has made significant contributions to our understanding of the mineralogical controls of mine-water geochemistry.

Acquisition and Evaluation of Thermodynamic Data for Bieberite-Moorhouseite Equilibria at 0.1 MPa

Abstract Published estimates for the equilibrium relative humidity (RH) at 25 °C for the reaction: bieberite (CoSO4·7H2O) = moorhouseite (CoSO4·6H2O) + H2O, range from 69.8 to 74.5%. To evaluate these data, the humidity-buffer technique was used to determine equilibrium constants for this reaction between 14 and 43 °C at 0.1 MPa. Reversals along five humidity-buffer curves yield ln K = 18.03–6509.43/T, where K is the equilibrium constant, and T is temperature in K. The derived standard Gibbs free energy of reaction is 9.43 kJ/mol, which agrees well with several previously reported values based on vaporpressure measurements. It also agrees well with values calculated from the data derived mostly from calorimetric measurements. Previous studies indicated that the temperature of the invariant point for the assemblage bieberite-moorhouseite-aqueous solution-vapor is near 44.7 °C, and our extrapolated data predict 91.1% RH at this temperature; the predicted position for the invariant point is in excellent agreement with those reported previously.

Evaluation of the sulfur isotopic composition and homogeneity of the Soufre de Lacq reference material

Sulfur isotopic analysis of the elemental sulfur reference material Soufre de Lacq, prepared as silver sulfide by chromous chloride reduction and as copper sulfide by sealed-tube synthesis, indicates that Soufre de Lacq is isotopically homogeneous across different size fractions to within analytical uncertainty (±0.15‰). The sulfur isotopic composition of aliquots of Soufre de Lacq prepared by these two techniques are identical to within analytical uncertainty. The mean sulfur isotopic composition for Soufre de Lacq prepared as silver sulfide and copper sulfide (relative to VCDT) is +16.20±0.15‰ (1σ).