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R. A. Ayuso

Publications and source records attributed to R. A. Ayuso.

At least 19 recordsLinked to original sources
USGS2022

Anthropogenic vs. natural pollution: An environmental study of an industrial site under remediation (Naples, Italy)

Heavy metal concentrations and Pb isotopic composition were determined in the soils, slags, scums and landfill materials from a shut down industrial (brownfield) site. This was the second largest integrated steelworks in Italy, and is now under remediation by a Government project. It is located in the outskirts of Napoli on the Bagnoli-Fuorigrotta plain (BFP), which is part of the Campi Flegrei (CF) volcanic caldera, where many spas and geothermal springs occur. The purpose of this work is to distinguish the natural (geogenic) component, originated by hydrothermal activity, from anthropogenic contamination owing to industrial activity. 'In-situ sediments' (soils), slags, scums and landfill materials from 20 drill-cores were selected from a network of 197 drills carried out on a 100 ?? 100 m grid, covering the entire brownfield site. In general, heavy metal enrichments in the upper 3 m of the cores strongly suggest mixing between natural (geogenic) and anthropogenic components. Pb isotopic data are suggestive of three potential end members, and confirm the existence of a strong natural component in addition to contamination from anthropogenic activities. The slags, scums and landfill materials have been proved, through mineralogy and leachate experiments, to be geochemically stable; this shows that metal pollutants are not bio-available and, hence, do not pose a risk to future developments on this site. The natural contribution of hydrothermal fluids to soil pollution, in addition to the non-bio-availability of metal pollutants from industrial materials, indicate that heavy metal remediation of soils in this area would be of little use. Continuous discharge from mineralized hydrothermal solutions would cancel out any remediation effort.

Geochemistry: Exploration, Environment, Analysis↗
USGS2011

Formation of cordierite-bearing lavas during anatexis in the lower crust beneath Lipari Island (Aeolian arc, Italy)

Cordierite-bearing lavas (CBL;~105 ka) erupted from the Mt. S. Angelo volcano at Lipari (Aeolian arc, Italy) are high-K andesites, displaying a range in the geochemical and isotopic compositions that reflect heterogeneity in the source and/or processes. CBL consist of megacrysts of Ca-plagioclase and clinopyroxene, euhedral crystals of cordierite and garnet, microphenocrysts of orthopyroxene and plagioclase, set in a heterogeneous rhyodacitic-rhyolitic groundmass containing abundant metamorphic and gabbroic xenoliths. New petrographic, chemical and isotopic data indicate formation of CBL by mixing of basaltic-andesitic magmas and high-K peraluminous rhyolitic magmas of anatectic origin and characterize partial melting processes in the lower continental crust of Lipari. Crustal anatectic melts generated through two main dehydration-melting peritectic reactions of metasedimentary rocks: (1) Biotite + Aluminosilicate + Quartz + Albite = Garnet + Cordierite + K-feldspar + Melt; (2) Biotite + Garnet + Quartz = Orthopyroxene + Cordierite + K-feldspar + Melt. Their position into the petrogenetic grid suggests that heating and consequent melting of metasedimentary rocks occurred at temperatures of 725 < T < 900°C and pressures of 0.4–0.45 GPa. Anatexis in the lower crust of Lipari was induced by protracted emplacement of basic magmas in the lower crust (~130 Ky). Crustal melting of the lower crust at 105 ka affected the volcano evolution, impeding frequent mafic-magma eruptions, and promoting magma stagnation and fractional crystallization processes.

Contributions to Mineralogy and Petrology↗
USGS2011

Geochemical and isotopic study of soils and waters from an Italian contaminated site: Agro Aversano (Campania)

Lead isotope applications have been widely used in recent years in environmental studies conducted on different kinds of sampled media. In the present paper, Pb isotope ratios have been used to determine the sources of metal pollution in soils and waters in the Agro Aversano area. During three different sampling phases, a total of 113 surface soils (5-20. cm), 20 samples from 2 soil profiles (0-1. m), 11 stream waters and 4 groundwaters were collected. Major element concentrations in sampled media have been analyzed by the ICP-MS technique. Surface soils (20 samples), all soil profiles and all waters have been also analyzed for Pb isotope compositions by thermal ionization (TIMS). The geochemical data were assessed using statistic methods and cartographically elaborated in order to have a clear picture of the level of disturbance of the area. Pb isotopic data were studied to discriminate between anthropogenic and geologic sources. Our results show that As (5.6-25.6. mg/kg), Cu (9-677. mg/kg), Pb (22-193. mg/kg), Tl (0.53-3.62. mg/kg), V (26-142. mg/kg) and Zn (34-215. mg//kg) contents in analyzed soils, exceed the intervention limits fixed by the Italian Environmental Law for residential areas in some of the sampled sites, while intervention limit for industrial areas is exceeded only for Cu concentrations. Lead isotopic data, show that there is a high similarity between the ratios measured in the leached soil samples and those deriving from anthropic activities. This similarity with anthropogenic Pb is also evident in the ratios measured in both groundwater and stream water samples. ?? 2010 Elsevier B.V.

Journal of Geochemical Exploration↗
USGS2008

The Ellsworth terrane, coastal Maine: Geochronology, geochemistry, and Nd-Pb isotopic composition - Implications for the rifting of Ganderia

The Ellsworth terrane is one of a number of fault-bounded blocks that occur along the eastern margin of Ganderia, the western-most of the peri-Gondwanan domains in the northern Appalachians that were accreted to Laurentia in the Paleozoic. Geologic relations, detrital zircon ages, and basalt geochemistry suggest that the Ellsworth terrane is part of Ganderia and not an exotic terrane. In the Penobscot Bay area of coastal Maine, the Ellsworth terrane is dominantly composed of bimodal basalt-rhyolite volcanic sequences of the Ellsworth Schist and unconformably overlying Castine Volcanics. We use new U-Pb zircon geochronology, geochemistry, and Nd and Pb isotopes for these volcanic sequences to constrain the petrogenetic history and paleotectonic setting of the Ellsworth terrane and its relationship with Ganderia. U-Pb zircon geochronology for rhyolites indicates that both the Ellsworth Schist (508.6 ?? 0.8 Ma) and overlying Castine Volcanics (503.5 ?? 2.5 Ma) are Middle Cambrian in age. Two tholefitic basalt types are recognized. Type Tb-1 basalt, present as pillowed and massive lava flows and as sills in both units, has depleted La and Ce ([La/Nd]N = 0.53-0.87) values, flat heavy rare earth element (REE) values, and no positive Th or negative Ta anomalies on primitive mantle-normalized diagrams. In contrast, type Th-2 basalt, present only in the Castine Volcanics, has stightly enriched LREE ([La/Yb]N = 1.42-2.92) values and no Th or Th anomalies. Both basalt types have strongly positive ??Nd (500) values (Th-1 = +7.9-+8.6; Th-2 = +5.6-+7.0) and relatively enriched Pb isotopic compositions (206Ph/204Pb = 18.037-19.784; 207/204Pb = 15.531-15.660; 2088Pb/204Pb = 37.810-38.817). The basalts have compositions transitional between recent normal and enriched mid-ocean-ridge basalt, and they were probably derived by partial melting of compositionatly heterogeneous asthenosphenc mantle. Two types of rhyolite also are present. Type R-1 rhyolite, which mostly occurs as tuffs interlayered with basalt in the Ellsworth Schist, is calc-alkaline and characterized by relatively low REE, Zr, and Hf contents, enriched LREE ([La/Yb]N ???3-6), positive Th and negative Th anomalies, ??Nd (500) values near zero (+0.5 to -0.9), and relatively unradiogenic Ph isotope values (206Pb/204Pb = 18.845; 207Pb/ 204Pb = 15.625; 208Pb/204Pb = 38.626). The data suggest that R-1 rhyolite magma was Likely derived by mixing of basalt with melts from a relatively depleted crustal source. Type R-2 rhyolite, which mostly occurs as lava flows and domes in the Castine volcanics, is tholeiitic and characterized by enriched REE with flat patterns ([La/Yb]N = 1-2.5), moderate negative Eu anomalies (Eu/Eu* = 0-34.5), enriched Th, small negative Th anomalies, and ??Nd (500) (+5.8-+7.5) and Ph isotope (206Pb/204Pb = 19.175-19.619; 207Pb/204Pb = 15.605--15.649; 208Pb/204Pb = 38.834-38.851) values that overlap those of the tholeiitic basalts. The data suggest that R-2 rhyolite magma was derived by the partial melting of hydrothermally altered basalt with the addition of a small amount of an enriched component, probably R-1 rhyolite. The geololic, geochemicai, and isotopic characteristics of the bimodal volcanic sequences strongly suggest that the Ellsworth terrane did not evolve as an extensional back-arc basin behind an active arc, but rather it evolved as a proto-oceanic rift petrogenetically similar to Cenozoic rifts like the Gulf of California-Salton mrough and Red Sea-Gulf of Aden rift systems. Such a setting is supported by the presence of serpentinized mantle and zinc-copper-rich massive sulfide deposits in the Ellsworth terrane. We conclude that the Ellsworth terrane developed as a Mid

Geological Society of America Bulletin↗
USGS2007

High arsenic concentrations and enriched sulfur and oxygen isotopes in a fractured-bedrock ground-water system

Ground water with high arsenic concentrations (up to 26.6????mol L- 1) has sulfate enriched in 34S and 18O in the fractured-bedrock, ground-water system of the Kelly's Cove watershed, Northport, Maine, USA. The ranges of sulfur and oxygen isotope values in aqueous sulfate, ??34S[SO4] and ??18O[SO4], at the Kelly's Cove watershed are + 3.4 to + 4.9??? and - 2.0 to + 6.7???, respectively. These isotope values are strikingly similar to those of the Goose River, Maine watershed which has ??34S[SO4] and ??18O[SO4] ranges of + 3.7 to + 4.6 ??? and - 2.6 to + 7.5???, respectively. In both systems, high arsenic concentrations occur with high ??34S[SO4] and ??18O[SO4] values, yet redox conditions and underlying rock types are quite different. The isotope values of sulfide minerals, ??34S[min], from four bedrock cores vary over short distances and range from - 5.1 to + 7.5???. The ??34S[SO4] values are controlled by the ??34S[min] values with minor input of atmospheric SO4. The much narrower range in ??34S[SO4] values than ??34S[min] values is probably due to sufficient ground-water mixing at a scale greater than the ??34S[min] variability. The ??34S[SO4] values are about 2??? higher than the average ??34S[min] value and fall within the range of ??34S[min] values, indicating only minor fractionation due to bacterial reduction of SO4. The highest ??18O[SO4] values were measured in the downgradient, confined, arsenic-rich ground water. High ??18O[SO4] values there cannot be due to aeration by atmospheric oxygen, but may arise from reoxidation of reduced SO4 products. The enrichment factors of ??18O in SO4 compared to H2O, + 7.2 to + 15.5???, in the Kelly's Cove ground water and the negligible 34S enrichment is very similar to those derived from experimental data of anaerobic sulfide oxidation in the presence of Mn and Fe oxides. Sea level at the Kelly's Cove watershed was approximately 80??m above present sea level about 13 000??years before present, imposing reducing conditions on that area of the watershed. Sea level dropped approximately 60??m below present sea level about 11 000??years before present, allowing for possible oxidation of sulfide minerals and precipitation of arsenic in ferric oxyhydroxides during aeration of the ground-water system. Under present redox conditions, there is evidence that bacteria reduction of ferric oxyhydroxides releases arsenic. The fractionation of 18O in the SO4 during anaerobic oxidation of sulfide in the presence of Mn and Fe oxides and subsequent release of arsenic during Mn and Fe oxide reduction may explain the relationship between high arsenic concentrations and elevated 18O[SO4] at Kelly's Cove. ?? 2007 Elsevier B.V. All rights reserved.

Chemical Geology↗
USGS2006

Crustal contamination and crystal entrapment during polybaric magma evolution at Mt. Somma-Vesuvius volcano, Italy: Geochemical and Sr isotope evidence

New major and trace element analyses and Sr-isotope determinations of rocks from Mt. Somma-Vesuvius volcano produced from 25 ky BP to 1944 AD are part of an extensive database documenting the geochemical evolution of this classic region. Volcanic rocks include silica undersaturated, potassic and ultrapotassic lavas and tephras characterized by variable mineralogy and different crystal abundance, as well as by wide ranges of trace element contents and a wide span of initial Sr-isotopic compositions. Both the degree of undersaturation in silica and the crystal content increase through time, being higher in rocks produced after the eruption at 472 AD (Pollena eruption). Compositional variations have been generally thought to reflect contributions from diverse types of mantle and crust. Magma mixing is commonly invoked as a fundamental process affecting the magmas, in addition to crystal fractionation. Our assessment of geochemical and Sr-isotopic data indicates that compositional variability also reflects the influence of crustal contamination during magma evolution during upward migration to shallow crustal levels and/or by entrapment of crystal mush generated during previous magma storage in the crust. Using a variant of the assimilation fractional crystallization model (Energy Conservation-Assimilation Fractional Crystallization; [Spera and Bohrson, 2001. Energy-constrained open-system magmatic processes I: General model and energy-constrained assimilation and fractional crystallization (EC-AFC) formulation. J. Petrol. 999-1018]; [Bohrson, W.A. and Spera, F.J., 2001. Energy-constrained open-system magmatic process II: application of energy-constrained assimilation-fractional crystallization (EC-AFC) model to magmatic systems. J. Petrol. 1019-1041]) we estimated the contributions from the crust and suggest that contamination by carbonate rocks that underlie the volcano (2 km down to 9-10 km) is a fundamental process controlling magma compositions at Mt. Somma-Vesuvius in the last 8 ky BP. Contamination in the mid- to upper crust occurred repeatedly, after the magma chamber waxed with influx of new mantle- and crustal-derived magmas and fluids, and waned as a result of magma withdrawal and production of large and energetic plinian and subplinian eruptions. ?? 2005 Elsevier B.V. All rights reserved.

LITHOS↗
USGS2006

Chapter 9 The magma feeding system of Somma-Vesuvius (Italy) strato-volcano: New inferences from a review of geochemical and Sr, Nd, Pb and O isotope data

A large database of major, trace and isotope (Sr, Nd, Pb, O) data exists for rocks produced by the volcanic activity of Somma-Vesuvius volcano. Variation diagrams strongly suggest a major role for evolutionary processes such as fractional crystallization, contamination, crystal trapping and magma maxing, occurring after magma genesis in the mantle. Most mafic magmas are enriched in LILE (Light Ion Lithophile Elements; K. Rb, Ba), REE (Ce, Sm) and Y, show small Nb−Ta negative anomalies, and have values of Nb/Zr at about 0.15. Enrichments in LILE, REE, Nb and Ta do not correlate with Sr isotope values or degree of both K enrichment and silica undersaturation. The results indicate mantle source heterogeneity produced by slab-derived components beneath the volcano. However, the Sr isotope values of Somma-Vesuvius increase from 0.7071 up to 0.7081 with transport through the uppermost 11–12 km of the crust. The Sr isotope variation suggests that the crustal component affected the magmas during ascent through the lithosphere to the surface. Our new geochemical assessment based on chemical, isotopic and fluid inclusion data points to the existence of three main levels of magma storage. Two of the levels are deep and may represent long-lived reservoirs; the uppermost crustal level probably coincides with the volcanic conduit. The deeper level of magma storage is deeper than 12 km and fed the 1944 AD eruption. The intermediate level coincides with the seismic discontinuity detected by Zollo et al. (1996) at about 8 km. This intermediate level supplies magmas with 87 Sr/ 86 Sr values between 0.7071 and 0.7074, and σO 18 <8% that typically erupted both during interplinian (i.e. 1906 AD) and sub-plinian (472 AD, 1631 AD) events. The shallowest level of magma storage at about 5 km was the site of magma chambers for the Pompei and Avellino plinian eruptions. New investigations are necessary to verify the proposed magma feeding system.

Somma-Vesuvius strato-volcano↗
USGS2004

Use of spatial statistics and isotopic tracers to measure the influence of arsenical pesticide use on stream sediment chemistry in New England, USA

Arsenical pesticides and herbicides, principally Pb arsenate, Ca arsenate, and Na arsenate with lesser use of other metal-As pesticides, were widely applied on apple, blueberry, and potato crops in New England during the first half of the twentieth century. Agricultural census data for this time period is used to define an agricultural index that identifies areas that are inferred to have used arsenical pesticides extensively. Factor analysis on metal concentrations in 1597 stream sediment samples collected throughout New England, grouped by agricultural-index categories, indicate a positive association of areas with stream sediment sample populations that contain higher As and Pb concentrations than samples from the region as a whole with sample site settings having high agricultural-index values. Population statistics for As and Pb concentrations and factor scores for an As-Pb factor all increase systematically and significantly with increasing agricultural-index intensity in the region, as tested by Kruskal-Wallis analysis. Lead isotope compositions for 16 stream sediments from a range of agricultural-index settings generally overlap the observed variation in rock sulfides and their weathering products; however, sediments collected from high agricultural-index settings have slightly more radiogenic Pb compositions, consistent with an industrial Pb contribution to these samples. Although weathering products from rocks are likely to be the dominant source of As and metals to most of the stream sediment samples collected in the region, the widespread use of arsenical pesticides and herbicides in New England during the early 1900-1960s appears to be a significant anthropogenic source of As and metals to many sediments in agricultural areas in the region and has raised background levels of As in some regions. Elevated concentrations of As in stream sediments are of concern for two reasons. Stream sediments with elevated As concentrations delineate areas with elevated background concentrations of As from both natural rock and anthropogenic sources that may contribute As to groundwater systems used for drinking water supplies. Conversion of agricultural land contaminated with arsenical pesticide residues to residential development may increase the likelihood that humans will be exposed to As. In addition, many stream sediment sites have As concentrations that exceed sediment quality guidelines established for freshwater ecosystems. Thirteen percent of the New England sediment sample sites exceed 9.79 mg/kg As, the threshold effects concentration (TEC), below which harmful effects are unlikely to be observed. Arsenic concentrations exceed 33 mg/kg, the probable effects concentration (PEC), above which harmful effects on sediment-dwelling organisms are expected to occur frequently, at 1.25% of the sediment sample sites. The sample sites that exceed the PEC value occur predominately in agricultural areas that used arsenical pesticides.

Conference Paper↗
USGS2004

Textural, compositional, and sulfur isotope variations of sulfide minerals in the Red Dog Zn-Pb-Ag deposits, Brooks Range, Alaska: Implications for Ore Formation

The Red Dog Zn-Pb deposits are hosted in organic-rich mudstone and shale of the Mississippian Kuna Formation. A complex mineralization history is defined by four sphalerite types or stages: (1) early brown sphalerite, (2) yellow-brown sphalerite, (3) red-brown sphalerite, and (4) late tan sphalerite. Stages 2 and 3 constitute the main ore-forming event and are volumetrically the most important. Sulfides in stages 1 and 2 were deposited with barite, whereas stage 3 largely replaces barite. Distinct chemical differences exist among the different stages of sphalerite. From early brown sphalerite to later yellow-brown sphalerite and red-brown sphalerite, Fe and Co content generally increase and Mn and Tl content generally decrease. Early brown sphalerite contains no more than 1.9 wt percent Fe and 63 ppm Co, with high Mn (up to 37 ppm) and Tl (126 ppm), whereas yellow-brown sphalerite and red-brown sphalerite contain high Fe (up to 7.3 wt %) and Co (up to 382 ppm), and low Mn (<27 ppm) and Tl (<37 ppm). Late tan sphalerite has distinctly lower Fe (< 0.9 wt %) and higher Tl (up to 355 ppm), Mn (up to 177 ppm), and Ge (426 ppm), relative to earlier sphalerite. Wide ranges in concentrations of Ag, Cu, Pb, and Sb characterize all sphalerite types, particularly yellow-brown sphalerite and red-brown sphalerite, and most likely reflect submicroscopic inclusions of galena, chalcopyrite and/or tetrahedrite in the sphalerite. In situ ion microprobe sulfur isotope analyses show a progression from extremely low ??34S values for stage 1 (as low as -37.20???) to much higher values for yellow-brown sphalerite (mean of 3.3???; n = 30) and red-brown sphalerite (mean of 3.4; n = 20). Late tan sphalerite is isotopically light (-16.4 to -27.2???). The textural, chem ical, and isotopic data indicate the following paragenesis: (1) deposition of early brown sphalerite with abundant barite, minor pyrite, and trace galena immediately beneath the sea floor in unconsolidated mud; (2) deposition of yellow-brown sphalerite during subsea-floor hydrothermal recrystallization and coarsening of preexisting barite; (3) open-space deposition of barite, red-brown sphalerite and other sulfides in veins and coeval replacement of barite; and (4) postore sulfide deposition, including the formation of late tan sphalerite breccias. Stage 1 mineralization took place in a low-temperature environment where fluids rich in Ba mixed with pore water or water-column sulfate to form barite, and metals combined with H2S derived from bacterial sulfate reduction to form sulfides. Higher temperatures and salinities and relatively oxidized ore-stage fluids (stages 2 and 3) compared with stage 1 were probably important controls on the abundances and relative amounts of metals in the fluids and the resulting sulfide chemistry. Textural observations and isotopic data show that preexisting barite was reductively dissolved, providing a source of H2S for sulfide mineral formation. In stage 3, the continued flow of hydrothermal fluids caused thermal alteration of organic-rich mudstones and a build-up of methane that led to fluid overpressuring, hydrofracturing, and vein formation. Barite, red-brown sphalerite, and other sulfides were deposited in the veins, and preexisting barite was pervasively replaced by red-brown sphalerite. Hydrothermal activity ceased until Jurassic time when thrusting and large-scale fluid flow related to the Brookian orogeny remobilized and formed late tan sphalerite in tectonic breccias. ?? 2004 by Economic Geology.

Economic Geology↗
USGS2001

Pb isotopes and toxic metals in floodplain and stream sediments from the Volturno river basin, Italy

We present results of a stratigraphic and environmental geochemistry study of the eastern sector of the Volturno river basin (Italy) using stream sediment and floodplain drill core samples. The cores, dated back to 7,000 years B.P., have been used to evaluate background (baseline) values. Pb isotopic compositions and toxic metal abundances have been determined to discriminate natural versus anthropogenic sources. The Pb isotopic compositions of the stream sediments overlap the values of Pb in petrol. The results from both stream sediment and drill core samples plot along a mixing line between the field that characterizes the volcanic rocks outcropping in the area (the natural component) and the Pb isotopic composition of petrol used in western Europe. Results suggest a prevalent contribution of the natural component for the Pb in the drill core samples and a prevailing anthropogenic component for the Pb isotopic compositions in the active stream sediments samples.

Environmental Geology↗
USGS2001

Major, trace element and isotope geochemistry (Sr-Nd-Pb) of interplinian magmas from Mt. Somma-Vesuvius (Southern Italy)

Major, trace element and isotopic (Sr, Nd, Pb) data are reported for representative samples of interplinian (Protohistoric, Ancient Historic and Medieval Formations) activity of Mt. Somma-Vesuvius volcano during the last 3500 years. Tephra and lavas exhibit significant major, trace element and isotopic variations. Integration of these data with those obtained by previous studies on the older Somma suites and on the latest activity, allows to better trace a complete petrological and geochemical evolution of the Mt. Somma-Vesuvius magmatism. Three main groups of rocks are recognized. A first group is older than 12.000 yrs, and includes effusive-explosive activity of Mt. Somma. The second group (8000-2700 yrs B.P.) includes the products emitted by the Ottaviano (8000 yrs. B.P.) and Avellino (3550 yrs B.P.) plinian eruptions and the interplinian activity associated with the Protohistoric Formation. Ancient Historic Formation (79-472 A.D.), Medieval Formation (472-1139 A.D.) and Recent interplinian activity (1631-1944 A.D.) belong to the third group of activity (79-1944 A.D.). The three groups of rocks display distinct positive trends of alkalis vs. silica, which become increasingly steeper with age. In the first group there is an increase in silica and alkalis with time, whereas an opposite tendency is observed in the two younger groups. Systematic variations are also evident among the incompatible (Pb, Zr, Hf, Ta, Th, U, Nb, Rb, Cs, Ba) and compatible elements (Sr, Co, Cr). REE document variable degrees of fractionation, with recent activity displaying higher La/Yb ratios than Medieval and Ancient Historic products with the same degree of evolution. N-MORB normalized multi-element diagrams for interplinian rocks show enrichment in Rb, Th, Nb, Zr and Sm (> *10 N-MORB). Sr isotope ratios are variable, with Protohistoric rocks displaying 87Sr/86Sr= 0.70711-0.70810, Ancient Historic 87Sr/86Sr=0.70665-0.70729, and Medieval 87Sr/86Sr=0.70685-0.70803. Neodymium isotopic compositions in the interplinian rocks show a tendency to become slightly more radiogenic with age, from the Protohistoric (143Nd/144Nd=0.51240-0.51247) to Ancient Historic (143Nd/144Nd=0.51245-0.51251). Medieval interplinian activity (143Nd/144Nd: 0.51250-0.51241) lacks meaningful internal trends. All the interplinian rocks have virtually homogeneous compositions of 207Pb/204Pb and 208Pb/204Pb in acid-leached residues (207Pb/204Pb ???15.633 to 15.687, 208Pb/204Pb ???38.947 to 39.181). Values of 206Pb/204Pb are very distinctive, however, and discriminate among the three interplinian cycles of activity (Protohistoric: 18.929-18.971, Ancient Historic: 19.018-19.088, Medieval: 18.964-19.053). Compositional trends of major, trace element and isotopic compositions clearly demonstrate strong temporal variations of the magma types feeding the Somma-Vesuvius activity. These different trends are unlikely to be related only to low pressure evolutionary processes, and reveal variations of parental melt composition. Geochemical data suggest a three component mixing scheme for the interplinian activity. These involve HIMU-type and DMM-type mantle and Calabrian-type lower crust. Interaction between these components has taken place in the source; however, additional quantitative constraints must be acquired in order to better discriminate between magma characteristics inherited from the sources and those acquired during shallow level evolution.

Mineralogy and Petrology↗
USGS2001

Isotope geochemistry and fluid inclusion study of skarns from Vesuvius

We present new mineral chemistry, fluid inclusion, stable carbon and oxygen, as well as Pb, Sr, and Nd isotope data of Ca-Mg-silicate-rich ejecta (skarns) and associated cognate and xenolithic nodules from the Mt. Somma-Vesuvius volcanic complex, Italy. The typically zoned skarn ejecta consist mainly of diopsidic and hedenbergitic, sometimes "fassaitic" clinopyroxene, Mg-rich and Ti-poor phlogopite, F-bearing vesuvianite, wollastonite, gehlenite, meionite, forsterite, clinohumite, anorthite and Mg-poor calcite with accessory apatite, spinell, magnetite, perovskite, baddeleyite, and various REE-, U-, Th-, Zr- and Ti-rich minerals. Four major types of fluid inclusions were observed in wollastonite, vesuvianite, gehlenite, clinopyroxene and calcite: a) primary silicate melt inclusions (THOM = 1000-1050??C), b) CO2 ?? H2S-rich fluid inclusions (THOM = 20-31.3??C into the vapor phase), c) multiphase aqueous brine inclusions (THOM = 720-820??C) with mainly sylvite and halite daughter minerals, and d) complex chloride-carbonate-sulfate-fluoride-silicate-bearing saline-melt inclusions (THOM = 870-890??C). The last inclusion type shows evidence for immiscibility between several fluids (silicate melt - aqueous chloride-rich liquid - carbonate/sulfate melt?) during heating and cooling below 870??C. There is no evidence for fluid circulation below 700??C and participation of externally derived meteoric fluids in skarn formation. Skarns have considerably variable 206Pb/204Pb (19.047-19.202), 207Pb/204Pb (15.655-15.670), and 208Pb/204Pb (38.915-39.069) and relatively low 143Nd/144Nd (0.51211-0.51244) ratios. The carbon and oxygen isotope compositions of skarn calcites (??13CV-PDB = -5.4 to -1.1???; ??18OV-SMOW = 11.7 to 16.4???) indicate formation from a 18O- and 13C-enriched fluid. The isotope composition of skarns and the presence of silicate melt inclusion-bearing wollastonite nodules suggests assimilation of carbonate wall rocks by the alkaline magma at moderate depths (< 5 km) and consequent exsolution of CO2-rich vapor and complex saline melts from the contaminated magma that reacted with the carbonate rocks to form skarns.

Mineralogy and Petrology↗
USGS2001

A metallogenic survey of alkalic rocks of Mt. Somma-Vesuvius volcano

Somma-Vesuvius is an alkaline volcano whose products (pumice, scoria and lava) have alkaline (Na2O+K2O) contents between 6 and 16 wt%, Mg number <50, SiO2 59-47 wt% and MgO 0-7.8 wt% (more than 50% of the samples have a content <2 wt%). Immobile-element ratios (Th/Yb, Ta/Yb, Ce/Yb) indicate a shoshonitic character, while the K2O content (4-10 wt%) is characteristic of ultrapotassic rocks. The behavior of selected metals is discussed by grouping them on the basis of the stratigraphic sequence and differentiating the volcanic activity between plinian and interplinian (Rolandi et al., 1998; Ayuso et al., 1998). This allows observation of the variation within each formation from 25.000y. BP to the last historic eruptive cycle (1631-1944 AD). The main processes to explain the wide distribution of the data presented are fractional crystallization of a mantle-derived magma, magma mixing, and contamination with heterogeneous lower and/or upper crust. Variation diagrams distinguish different behavior for groups of metals: Ag (0.01-0.2 ppm), Mo (1-8.8 ppm), W (1.3-13 ppm), Pb (16-250 ppm), Sb (0.2-2.6 ppm), Sc (0.2-61 ppm), Li (15-140 ppm) and Be (1-31 ppm) increase with increasing differentiation and tend to correlate with the incompatible trace elements (Th, Hf, etc). Cu (10-380 ppm), Au (2-143 ppb), Co (0.7-35.1 ppm) and Fe (1.3-6.2 wt%) decrease towards advanced stage of differentiation. Iron also identifies three magmatic groups. The ratio Fe3+/Fe2+ ranges between 0.2 and 1.8, and Fe2O3/ (Fe2O3+FeO) ranges between 0.2 and 0.8, giving rise to an oxidized environment; exceptions are in the samples belonging to the interplinian formations: I, II, medieval and 1631-1994 AD. Fluorine ranges between 0.1 and 0.4 wt% for the complete Mt. Somma-Vesuvius activity, except for the Ottaviano and Avellino plinian (0.8 wt%) events. Chlorine has a wider range, from 0.1 wt% to 1.6 wt%. Mt Somma-Vesuvius has some features similar to those of mineralized alkaline magmatic systems which coincide with the transition between subduction-related compression and extension-related to continental rifting. We infer that a prospective time for the formation of mineralization at Mt Somma-Vesuvius was during the 1631-1944 eruptive period.

Mineralogy and Petrology↗
USGS2001

Remnant colloform pyrite at the haile gold deposit, South Carolina: A textural key to genesis

Auriferous iron sulfide-bearing deposits of the Carolina slate belt have distinctive mineralogical and textural features-traits that provide a basis to construct models of ore deposition. Our identification of paragenetically early types of pyrite, especially remnant colloform, crustiform, and layered growth textures of pyrite containing electrum and pyrrhotite, establishes unequivocally that gold mineralization was coeval with deposition of host rocks and not solely related to Paleozoic tectonic events. Ore horizons at the Haile deposit, South Carolina, contain many remnants of early pyrite: (1) fine-grained cubic pyrite disseminated along bedding; (2) fine- grained spongy, rounded masses of pyrite that may envelop or drape over pyrite cubes; (3) fragments of botryoidally and crustiform layered pyrite, and (4) pyritic infilling of vesicles and pumice. Detailed mineral chemistry by petrography, microprobe, SEM, and EDS analysis of replaced pumice and colloform structures containing both arsenic compositional banding and electrum points to coeval deposition of gold and the volcanic host rocks and, thus, confirms a syngenetic origin for the gold deposits. Early pyrite textures are present in other major deposits of the Carolina slate belt, such as Ridgeway and Barite Hill, and these provide strong evidence for models whereby the sulfide ores formed prior to tectonism. The role of Paleozoic metamorphism was to remobilize and concentrate gold and other minerals in structurally prepared sites. Recognizing the significance of paragenetically early pyrite and gold textures can play an important role in distinguishing sulfide ores that form in volcanic and sedimentary environments from those formed solely by metamorphic processes. Exploration strategies applied to the Carolina slate belt and correlative rocks in the eastern United States in the Avalonian basement will benefit from using syngenetic models for gold mineralization.

Economic Geology↗
USGS2000

Stratigraphy, geochemistry and tectonic significance of the Oligocene magmatic rocks of western Oaxaca, southern Mexico

In Western Oaxaca, Tertiary magmatic activity is represented by extensive plutons along the continental margin and volcanic sequences in the inland region. K-Ar age determinations reported previously and in the present work indicate that these rocks correspond to a relatively broad arc in this region that was active mainly during the Oligocene (~ 35 to ~ 25 Ma). In the northern sector of western Oaxaca (Huajuapan-Monte Verde-Yanhuitlan), the volcanic suite comprises principally basaltic andesite to andesitic lavas, overlying minor silicic to intermediate volcaniclastic rocks (epiclastic deposits, ash fall tuffs, ignimbrites) that were deposited in the lacustrine-fluvial environment. The southern sector of the volcanic zone includes the Tlaxiaco-Laguna de Guadalupe region and consists of intermediate to silicic pyroclastic and epiclastic deposits, with silicic ash fall tuffs and ignimbrites. In both sectors, numerous andesitic to dacitic hypabyssal intrusions (stocks and dikes) were emplaced at different levels of the sequence. The granitoids of the coastal plutonic belt are generally more differentiated than the volcanic rocks that predominate in the northern sector and vary in composition from granite to granodiorite. The studied rocks show large-ion lithophile element (LILE) enrichment (K, Rb, Ba, Th) relative to high-field-strength (HFS) elements (Nb, Ti, Zr) that is characteristic of subduction-related magmatic rocks. On chondrite-normalized rare earth element diagrams, these samples display light rare earth element enrichment (LREE) and a flat pattern for the heavy rare earth elements (HREE). In spite of the contrasting degree of differentiation between the coastal plutons and inland volcanic rocks, there is a relatively small variation in the isotopic composition of these two suites. Initial 87Sr/86Sr ratios obtained and reported previously for Tertiary plutonic rocks of western Oaxaca range from 0.7042 to 0.7054 and ??Nd values, from -3.0 to +2.4, and for the volcanic rocks, from 0.7042 to 0.7046 and 0 +2.6. The range of these isotope ratios and those reported for the basement rocks in this region suggest a relatively low degree of old crustal involvement for most of the studied rocks. The Pb isotopic compositions of the Tertiary magmatic rocks also show a narrow range [(206Pb/204Pb) = 18.67-18.75; (207Pb/204Pb) = 15.59-15.62; (208Pb/204Pb) = 38.44-38.59], suggesting a similar source region for the volcanic and plutonic rocks. Trace elements and isotopic compositions suggest a mantle source in the subcontinental lithosphere that has been enriched by a subduction component. General tectonic features in this region indicate a more active rate of transtensional deformation for the inland volcanic region than along the coastal margin during the main events of Oligocene magmatism. The lower degree of differentiation of the inland volcanic sequences, particularly the upper unit of the northern sector, compared to the plutons of the coastal margin, suggests that the differentiation of the Tertiary magmas in southern Mexico was controlled to a great extent by the characteristics of the different strain domains. (C) 2000 Elsevier Science B.V. All rights reserved.

Conference Paper↗
USGS1998

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

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 value are ???50. Internally gradational chemical groups or cycles are distinguished by age: (1) 25 000 to 14 000 yr B.P.; (2) 8000 yr B.P. to A.D. 79; and (3) A.D. 79 to 1944. A small number of lavas, dikes and scora were also analysed from the Somma formation (~ 35 000 to 25 000 yr B.P.). Within each group, contents of Na2O + K2O increas with decreasing MgO along distinct rocks. Nb/Y values are variable from 0.66 to 3.14 (at SiO2 ??? 50 wt%) generally in the range of alkaline and ultra-alkaline rocks. Variations in contents of some majro elements (e.g., P and Ti), and trace elements (e.g., Th, Nb, Ta, Zr, Hf, Pb, La, and Sc), as well as contrasting trends in ratios of various elements (e.g., Ta/Yb, Hf/U, Th/Ta, Th/Hf, Th/Yb, etc.) are also generally consistent with the group subdivisions. For example, Th/Hf increases from ??? 5 to ??? 10 with decreasing age for the Vesuvius system as a whole, yielding similar compositions in the least evolved rocks (low-silica, high-MgO, imcompatible element-poor) erupted at the end of each cycle. Internal variations within individual eruptions also systematically changed generally towards a common mafic composition at the end of each cycle, thus reflecting the dominanit 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 other 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 the light rare-earth elements; deep Nb and Ta netgative 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 (87Sr/86Sr ~ 0.70699 to 0.70803) and with contributions from several isotopic components. Isotopic compositions for ??18O (7.3 to 10.2%), Pb for mineral separates and whole rocks (206Pb/204Pb ~ 18.947 to 19.178, 207Pb/204/Pb ~ 15.617 to 15.769, 208Pb/204Pb ~38.915 to 39.345), and Nd (143Nd ~ 0.51228 to 0.51251) also show variability. Oxygen isotope data show that pumices have higher ??18O values than cogenetic lavas, and that ??18O 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.

Journal of Volcanology and Geothermal Research↗