Richard Hervig | Arizona State University (original) (raw)

Papers by Richard Hervig

Research paper thumbnail of Isotopic and elemental partitioning of boron between hydrous fluid and silicate melt

American Mineralogist, 2002

Research paper thumbnail of Hervig 1986 LherzoliteChemistry

Trans R. Soc. Edinburgh, 1986

ABSTRACT: Electron and ion microprobe analyses for P, Si, Ti, Al, Cr, V, Sc, Fe, Mn, Mg, Ni, Co, ... more ABSTRACT: Electron and ion microprobe analyses for P, Si, Ti, Al, Cr, V, Sc, Fe, Mn, Mg, Ni, Co, Ca, Sr, Na, Kand Li in olivine, pyroxenes and garnet in forty-two cold and twelve hot garnet lherzolites from kimberlites, nine spinel lherzolites from kimberlites and eighteen from alkali basalts, and one cold garnet lherzolite from the Malaita alnoite, are compared with published data for minerals occurring in lherzolite, harzburgite and eclogite xenoliths, for silicate megacrysts in kimberlites, and for silicate inclusions in diamonds. Despite wide ranges in the chemistry of minerals from garnet and spinel lherzolites, there are distinct regions in composition space that would enable determination of the parent lithology of disaggregated minerals in kimberlites and alkali basalts. Titanium correlates with Fe3+ in garnets. Chromium, Al, V and Sc are distributed similarly between silicates in lherzolites. Sodium correlates with trivalent ions in olivine, and increases with temperature. The distribution of Na, but not of K and Li, between olivine and clinopyroxene correlates with temperature. The regular partitioning of Ti, Mn and Ni places constraints on crystal-liquid partition coefficients. Above the stability temperature of mica, 'metasomatising fluids' may scavenge Cr and other trivalent ions as they increase Ti in silicates.
KEY WORDS: aluminum, chromium, iron, lithium, nickel, potassium, scandium, sodium, titanium, vanadium.

Research paper thumbnail of Implications of Trace Element Zoning in Deformed Quartz from the Santa Catalina Mylonite Zone

Journal of Geology, 1989

ABSTRACT

Research paper thumbnail of Boron isotopic composition of subduction-zone metamorphic rocks

Chemical Geology, 1999

... Ishikawa and Nakamura (1993) have shown that ancient marine sediments have systematically low... more ... Ishikawa and Nakamura (1993) have shown that ancient marine sediments have systematically lower δ 11 B values than modern sediments ... eclogites from the Franciscan Complex and Catalina Schist (California) and a coesite-bearing eclogite from Dora Maira (western Alps ...

Research paper thumbnail of Reference Minerals for the Microanalysis of Light Elements

Geostandards Newsletter-the Journal of Geostandards and Geoanalysis, 2001

The quantitative determination of light element concentrations in geological specimens represents... more The quantitative determination of light element concentrations in geological specimens represents a major analytical challenge as the electron probe is generally not suited to this task. With the development of new in situ analytical techniques, and in particular the increasing use of secondary ion mass spectrometry, the routine determination of Li, Be and B contents has become a realistic goal. However, a major obstacle to the development of this research field is the critical dependence of SIMS on the availability of well characterized, homogeneous reference materials that are closely matched in matrix (composition and structure) to the sample being studied. Here we report the first results from a suite of large, gem crystals which cover a broad spectrum of minerals in which light elements are major constituents. We have characterized these materials using both in situ and wet chemical techniques. The samples described here are intended for distribution to geochemical laboratories active in the study of light elements. Further work is needed before reference values for these materials can be finalized, but the availability of this suite of materials represents a major step toward the routine analysis of the light element contents of geological specimens.La détermination quantitative des concentrations en éléments légers dans les échantillons géologiques représente un défi analytique majeur, la sonde électronique ne convenant généralement pas pour ce travail. Avec le développement de nouvelles techniques analytiques in situ, en particulier l'utilisation grandissante de la spectrométrie ionique secondaire, la détermination en routine des teneurs en Li, Be et B est devenue un objectif réaliste. Toutefois, un obstacle majeur dans le développement de cette recherche subsiste : la technique SIMS est dépendante de la disponibilité de matériaux de référence bien caractérisés et homogènes proches en composition et en structure de l'échantillon étudié. Nous rapportons ici les premiers résultats obtenus à partie d'un groupe de grands cristaux de qualité gemme recouvrant un large spectre de minéraux composés essentiellement d'éléments légers. Nous avons caractérisé ces matériaux en utilisant à la fois des techniques in situ et par voie humide. Les échantillons décrits ici vont être distribués dans les laboratoires de géochimie spécialisés dans l'étude des éléments légers. Avant la conclusion des valeurs de référence de ces matériaux, des travaux ultérieurs seront nécessaires, mais la disponibilité de l'ensemble de ces matériaux représente une étape importante vers l'analyse en routine des teneurs en éléments légers d'échantillons géologiques.

Research paper thumbnail of Diffusion Kinetics of Samarium and Neodymium in Garnet, and a Method

Science, 1998

Experimental determinations of the diffusion coefficients of samarium and neodymium in almandine ... more Experimental determinations of the diffusion coefficients of samarium and neodymium in almandine garnet and theoretical considerations show that one cannot assign a sufficiently restricted range of closure temperature, TC, to the samarium-neodymium decay system in garnet for the purpose of constraining the cooling rate. However, it is shown that the samarium-neodymium cooling age of garnet can be used to calculate both cooling rate and TC if the temperature and age at the peak metamorphic conditions are known.

Research paper thumbnail of Rare earth diffusion kinetics in garnet: Experimental studies and applications

Geochimica Et Cosmochimica Acta, 2005

We determined the diffusion coefficient of Sm in almandine garnet as function of temperature at 1... more We determined the diffusion coefficient of Sm in almandine garnet as function of temperature at 1 bar and fO 2 corresponding to that of wüstite-iron buffer, and to a limited extent, that of a few other selected rare earth elements in almandine and pyrope garnets. Both garnets were demonstrated to have metastably survived the diffusion annealing at conditions beyond their stability fields. The experimental diffusion profiles were analyzed by secondary ion mass spectrometry, and in addition, by Rutherford back scattering spectroscopy for two samples. Transmission electron microscopic study of an almandine crystal that was diffusionannealed did not reveal any near-surface fast diffusion path. Using reasonable approximations and theoretical analysis of vacancy diffusion, the experimental data were used to develop an expression of rare earth element (REE) diffusion coefficient in garnet as a function of temperature, pressure, fO 2 , ionic radius, and matrix composition. Calculation of the closure temperature for the Sm-Nd decay system in almandine garnet in a metamorphic terrain shows very good agreement with that constrained independently. Modeling of the REE evolution in melt and residual garnet suggests that for dry melting condition, the REE pattern in the melt should commonly conform closely to that expected for equilibrium melting. However, for much lower solidus temperatures that would prevail in the presence of a H 2 O-CO 2 fluid, the concentration of light REE in the melt could be significantly lower than that under equilibrium melting condition. A reported core and rim differences in the REE content of a garnet crystal in a mantle xenolith in kimberlite have been reproduced by assuming that the REE zoning was a consequence of entrapment in a magma derived from an external source for ϳ32,000 yr before the eruption.

Research paper thumbnail of Melt-vapor solubilities and elemental partitioning in peraluminous granite-pegmatite systems: experimental results with Macusani glass at 200 MPa

Contributions To Mineralogy and Petrology, 1988

Vapor-saturated experiments at 200 MPa with peraluminous, lithophile-element-rich rhyolite obsidi... more Vapor-saturated experiments at 200 MPa with peraluminous, lithophile-element-rich rhyolite obsidian from Macusani, Peru, reveal high miscibility of H2O and silicate melt components. The H2O content of melt at saturation (11.5+-0.5 wt.%) is almost twice that predicted by existing melt speciation models. The corresponding solubility of melt components in vapor decreases from 15 wt.% dissolved solids (750°–775° C) to 9 wt.% at 600° C. With regard to major and most minor components, macusanite melt dissolves congruently in vapor. Among the elements studied (B, P, F, Li, Rb, Cs, Be, Sr, Ba, Nb, Zr, Hf, Y, Pb, Th, U, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, and Tm), only boron has a vapor/melt partition coefficient (D[B]) consistently ≥1 at superliquidus temperatures (>645° C). Phosphorus and fluorine behave similarly, with D[P] and D[F]<0.5. Little or no significant vapor/melt fractionation is evident among most periodic groups (alkalis, alkaline earths, Zr/Hf, or the REE). The temperature dependence of vapor/melt partition coefficients is generally greatest for cations with charge ≥ +3 (except Nb and U); most vapor/melt partition coefficients for trace elements increase with decreasing temperature to the liquidus. Crystallization proceeds by condensation of crystalline phases from vapor; most coexisting melts are aphyric. Changes in the major element content of melt are dominated by the mineral assemblage crystallized from vapor, which includes subequal proportions of white mica, quartz, albite, and orthoclase. The volumetric proportion of (mica + or-thoclase)/albite increases slightly with decreasing T, creating a sodic, alkaline vapor. Vapor deposition of topaz (T≤500° C), which consumes F from melt, returns K/Na ratios of melt to near unity with the vapor-deposition of albite. The abundances of most trace elements in residual melt change little with the crystallization of major phases, but in some cases are strongly controlled by the deposition of accessory phases including apatite (T≤550° C), which depletes the melt in P and REE. Below the liquidus, boron increasingly favors the vapor over melt with decreasing temperatures.

Research paper thumbnail of Vapor-undersaturated experiments with Macusani glass+H 2 O at 200 MPa, and the internal differentiation of granitic pegmatites

Contributions To Mineralogy and Petrology, 1989

Vapor-undersaturated fractional crystallization experiments with Macusani glass (macusanite), a p... more Vapor-undersaturated fractional crystallization experiments with Macusani glass (macusanite), a peraluminous rhyolite obsidian, at 200 MPa yield mineralogical fabrics and zonation, and melt fractionation trends that closely resemble those found in zoned granitic pegmatites and other granitoids of comparable composition (typically peraluminous, Li-Be-Ta-rich deposits). The zonation from the edge of charges inward is characterized by: (1) fine-grained sodic feldspar-quartz border zones; (2) a fringe of very coarse-grained graphic quartz-feldspar intergrowths that flair radially toward melt and terminate with nearly monophase K-feldspar; (3) cores of very coarse-grained, nearly monominerallic quartz or virgilite (LiAlSi5O12)±mica; and (4) late-stage, fine-grained albite+mica intergrowths that are deposited from alkaline, Na-rich interstitial melt at vapor saturation. Similar experimental products have been observed in compositionally simpler, less evolved systems. Liquid lines of descent from initially H2O-undersaturated runs are marked by a decrease in SiO2, and increases in Na/K, B, P, F, H2O, and a variety of trace lithophile cations. These trends are believed to be governed by three factors: (1) disequilibrium growth of feldspars (±quartz) via metastable supersaturation; (2) fractionation of melt toward SiO2-depleted, Na-rich compositions due to increases in B, P, and F; and (3) changes in nucleation and growth rates, mostly as a function of the H2O content of melt (X wm). In contrast, experiments that are cooled below the liquidus from the field of melt+aqueous vapor (London et al. 1988) fail to replicate pegmatitic characteristics in most respects. On the basis of these and other experiments, we suggest that the formation of pegmatite fabrics stems primarily from fractional crystallization in volatile-rich melts, and that enrichments in normally trace lithophile elements result from melt differentiation trends toward increasingly alkaline, silica-depleted compositions. Although vapor saturation at near-solidus and subsolidus conditions may promote extensive recrystallization, an aqueous vapor phase does not appear to be necessary for the generation of most of the salient characteristics of pegmatites.

Research paper thumbnail of Isotopic and elemental partitioning of boron between hydrous fluid and silicate melt

American Mineralogist, 2002

Research paper thumbnail of Hervig 1986 LherzoliteChemistry

Trans R. Soc. Edinburgh, 1986

ABSTRACT: Electron and ion microprobe analyses for P, Si, Ti, Al, Cr, V, Sc, Fe, Mn, Mg, Ni, Co, ... more ABSTRACT: Electron and ion microprobe analyses for P, Si, Ti, Al, Cr, V, Sc, Fe, Mn, Mg, Ni, Co, Ca, Sr, Na, Kand Li in olivine, pyroxenes and garnet in forty-two cold and twelve hot garnet lherzolites from kimberlites, nine spinel lherzolites from kimberlites and eighteen from alkali basalts, and one cold garnet lherzolite from the Malaita alnoite, are compared with published data for minerals occurring in lherzolite, harzburgite and eclogite xenoliths, for silicate megacrysts in kimberlites, and for silicate inclusions in diamonds. Despite wide ranges in the chemistry of minerals from garnet and spinel lherzolites, there are distinct regions in composition space that would enable determination of the parent lithology of disaggregated minerals in kimberlites and alkali basalts. Titanium correlates with Fe3+ in garnets. Chromium, Al, V and Sc are distributed similarly between silicates in lherzolites. Sodium correlates with trivalent ions in olivine, and increases with temperature. The distribution of Na, but not of K and Li, between olivine and clinopyroxene correlates with temperature. The regular partitioning of Ti, Mn and Ni places constraints on crystal-liquid partition coefficients. Above the stability temperature of mica, 'metasomatising fluids' may scavenge Cr and other trivalent ions as they increase Ti in silicates.
KEY WORDS: aluminum, chromium, iron, lithium, nickel, potassium, scandium, sodium, titanium, vanadium.

Research paper thumbnail of Implications of Trace Element Zoning in Deformed Quartz from the Santa Catalina Mylonite Zone

Journal of Geology, 1989

ABSTRACT

Research paper thumbnail of Boron isotopic composition of subduction-zone metamorphic rocks

Chemical Geology, 1999

... Ishikawa and Nakamura (1993) have shown that ancient marine sediments have systematically low... more ... Ishikawa and Nakamura (1993) have shown that ancient marine sediments have systematically lower δ 11 B values than modern sediments ... eclogites from the Franciscan Complex and Catalina Schist (California) and a coesite-bearing eclogite from Dora Maira (western Alps ...

Research paper thumbnail of Reference Minerals for the Microanalysis of Light Elements

Geostandards Newsletter-the Journal of Geostandards and Geoanalysis, 2001

The quantitative determination of light element concentrations in geological specimens represents... more The quantitative determination of light element concentrations in geological specimens represents a major analytical challenge as the electron probe is generally not suited to this task. With the development of new in situ analytical techniques, and in particular the increasing use of secondary ion mass spectrometry, the routine determination of Li, Be and B contents has become a realistic goal. However, a major obstacle to the development of this research field is the critical dependence of SIMS on the availability of well characterized, homogeneous reference materials that are closely matched in matrix (composition and structure) to the sample being studied. Here we report the first results from a suite of large, gem crystals which cover a broad spectrum of minerals in which light elements are major constituents. We have characterized these materials using both in situ and wet chemical techniques. The samples described here are intended for distribution to geochemical laboratories active in the study of light elements. Further work is needed before reference values for these materials can be finalized, but the availability of this suite of materials represents a major step toward the routine analysis of the light element contents of geological specimens.La détermination quantitative des concentrations en éléments légers dans les échantillons géologiques représente un défi analytique majeur, la sonde électronique ne convenant généralement pas pour ce travail. Avec le développement de nouvelles techniques analytiques in situ, en particulier l'utilisation grandissante de la spectrométrie ionique secondaire, la détermination en routine des teneurs en Li, Be et B est devenue un objectif réaliste. Toutefois, un obstacle majeur dans le développement de cette recherche subsiste : la technique SIMS est dépendante de la disponibilité de matériaux de référence bien caractérisés et homogènes proches en composition et en structure de l'échantillon étudié. Nous rapportons ici les premiers résultats obtenus à partie d'un groupe de grands cristaux de qualité gemme recouvrant un large spectre de minéraux composés essentiellement d'éléments légers. Nous avons caractérisé ces matériaux en utilisant à la fois des techniques in situ et par voie humide. Les échantillons décrits ici vont être distribués dans les laboratoires de géochimie spécialisés dans l'étude des éléments légers. Avant la conclusion des valeurs de référence de ces matériaux, des travaux ultérieurs seront nécessaires, mais la disponibilité de l'ensemble de ces matériaux représente une étape importante vers l'analyse en routine des teneurs en éléments légers d'échantillons géologiques.

Research paper thumbnail of Diffusion Kinetics of Samarium and Neodymium in Garnet, and a Method

Science, 1998

Experimental determinations of the diffusion coefficients of samarium and neodymium in almandine ... more Experimental determinations of the diffusion coefficients of samarium and neodymium in almandine garnet and theoretical considerations show that one cannot assign a sufficiently restricted range of closure temperature, TC, to the samarium-neodymium decay system in garnet for the purpose of constraining the cooling rate. However, it is shown that the samarium-neodymium cooling age of garnet can be used to calculate both cooling rate and TC if the temperature and age at the peak metamorphic conditions are known.

Research paper thumbnail of Rare earth diffusion kinetics in garnet: Experimental studies and applications

Geochimica Et Cosmochimica Acta, 2005

We determined the diffusion coefficient of Sm in almandine garnet as function of temperature at 1... more We determined the diffusion coefficient of Sm in almandine garnet as function of temperature at 1 bar and fO 2 corresponding to that of wüstite-iron buffer, and to a limited extent, that of a few other selected rare earth elements in almandine and pyrope garnets. Both garnets were demonstrated to have metastably survived the diffusion annealing at conditions beyond their stability fields. The experimental diffusion profiles were analyzed by secondary ion mass spectrometry, and in addition, by Rutherford back scattering spectroscopy for two samples. Transmission electron microscopic study of an almandine crystal that was diffusionannealed did not reveal any near-surface fast diffusion path. Using reasonable approximations and theoretical analysis of vacancy diffusion, the experimental data were used to develop an expression of rare earth element (REE) diffusion coefficient in garnet as a function of temperature, pressure, fO 2 , ionic radius, and matrix composition. Calculation of the closure temperature for the Sm-Nd decay system in almandine garnet in a metamorphic terrain shows very good agreement with that constrained independently. Modeling of the REE evolution in melt and residual garnet suggests that for dry melting condition, the REE pattern in the melt should commonly conform closely to that expected for equilibrium melting. However, for much lower solidus temperatures that would prevail in the presence of a H 2 O-CO 2 fluid, the concentration of light REE in the melt could be significantly lower than that under equilibrium melting condition. A reported core and rim differences in the REE content of a garnet crystal in a mantle xenolith in kimberlite have been reproduced by assuming that the REE zoning was a consequence of entrapment in a magma derived from an external source for ϳ32,000 yr before the eruption.

Research paper thumbnail of Melt-vapor solubilities and elemental partitioning in peraluminous granite-pegmatite systems: experimental results with Macusani glass at 200 MPa

Contributions To Mineralogy and Petrology, 1988

Vapor-saturated experiments at 200 MPa with peraluminous, lithophile-element-rich rhyolite obsidi... more Vapor-saturated experiments at 200 MPa with peraluminous, lithophile-element-rich rhyolite obsidian from Macusani, Peru, reveal high miscibility of H2O and silicate melt components. The H2O content of melt at saturation (11.5+-0.5 wt.%) is almost twice that predicted by existing melt speciation models. The corresponding solubility of melt components in vapor decreases from 15 wt.% dissolved solids (750°–775° C) to 9 wt.% at 600° C. With regard to major and most minor components, macusanite melt dissolves congruently in vapor. Among the elements studied (B, P, F, Li, Rb, Cs, Be, Sr, Ba, Nb, Zr, Hf, Y, Pb, Th, U, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, and Tm), only boron has a vapor/melt partition coefficient (D[B]) consistently ≥1 at superliquidus temperatures (>645° C). Phosphorus and fluorine behave similarly, with D[P] and D[F]<0.5. Little or no significant vapor/melt fractionation is evident among most periodic groups (alkalis, alkaline earths, Zr/Hf, or the REE). The temperature dependence of vapor/melt partition coefficients is generally greatest for cations with charge ≥ +3 (except Nb and U); most vapor/melt partition coefficients for trace elements increase with decreasing temperature to the liquidus. Crystallization proceeds by condensation of crystalline phases from vapor; most coexisting melts are aphyric. Changes in the major element content of melt are dominated by the mineral assemblage crystallized from vapor, which includes subequal proportions of white mica, quartz, albite, and orthoclase. The volumetric proportion of (mica + or-thoclase)/albite increases slightly with decreasing T, creating a sodic, alkaline vapor. Vapor deposition of topaz (T≤500° C), which consumes F from melt, returns K/Na ratios of melt to near unity with the vapor-deposition of albite. The abundances of most trace elements in residual melt change little with the crystallization of major phases, but in some cases are strongly controlled by the deposition of accessory phases including apatite (T≤550° C), which depletes the melt in P and REE. Below the liquidus, boron increasingly favors the vapor over melt with decreasing temperatures.

Research paper thumbnail of Vapor-undersaturated experiments with Macusani glass+H 2 O at 200 MPa, and the internal differentiation of granitic pegmatites

Contributions To Mineralogy and Petrology, 1989

Vapor-undersaturated fractional crystallization experiments with Macusani glass (macusanite), a p... more Vapor-undersaturated fractional crystallization experiments with Macusani glass (macusanite), a peraluminous rhyolite obsidian, at 200 MPa yield mineralogical fabrics and zonation, and melt fractionation trends that closely resemble those found in zoned granitic pegmatites and other granitoids of comparable composition (typically peraluminous, Li-Be-Ta-rich deposits). The zonation from the edge of charges inward is characterized by: (1) fine-grained sodic feldspar-quartz border zones; (2) a fringe of very coarse-grained graphic quartz-feldspar intergrowths that flair radially toward melt and terminate with nearly monophase K-feldspar; (3) cores of very coarse-grained, nearly monominerallic quartz or virgilite (LiAlSi5O12)±mica; and (4) late-stage, fine-grained albite+mica intergrowths that are deposited from alkaline, Na-rich interstitial melt at vapor saturation. Similar experimental products have been observed in compositionally simpler, less evolved systems. Liquid lines of descent from initially H2O-undersaturated runs are marked by a decrease in SiO2, and increases in Na/K, B, P, F, H2O, and a variety of trace lithophile cations. These trends are believed to be governed by three factors: (1) disequilibrium growth of feldspars (±quartz) via metastable supersaturation; (2) fractionation of melt toward SiO2-depleted, Na-rich compositions due to increases in B, P, and F; and (3) changes in nucleation and growth rates, mostly as a function of the H2O content of melt (X wm). In contrast, experiments that are cooled below the liquidus from the field of melt+aqueous vapor (London et al. 1988) fail to replicate pegmatitic characteristics in most respects. On the basis of these and other experiments, we suggest that the formation of pegmatite fabrics stems primarily from fractional crystallization in volatile-rich melts, and that enrichments in normally trace lithophile elements result from melt differentiation trends toward increasingly alkaline, silica-depleted compositions. Although vapor saturation at near-solidus and subsolidus conditions may promote extensive recrystallization, an aqueous vapor phase does not appear to be necessary for the generation of most of the salient characteristics of pegmatites.