Inter‐laboratory Characterisation of Apatite Reference Materials for Chlorine Isotope Analysis

Here we report on a set of six apatite reference materials (chlorapatites MGMH#133648, TUBAF#38 and fluorapatites MGMH#128441A, TUBAF#37, 40, 50) which we have characterised for their chlorine isotope ratios; these RMs span a range of Cl mass fractions within the apatite Ca₁₀(PO₄)₆(F,Cl,OH)₂ solid solution series. Numerous apatite specimens, obtained from mineralogical collections, were initially screened for ³⁷Cl/³⁵Cl homogeneity using SIMS followed by δ³⁷Cl characterisation by gas source mass spectrometry using both dual‐inlet and continuous‐flow modes. We also report major and key trace element compositions as determined by EPMA. The repeatability of our SIMS results was better than ± 0.10‰ (1s) for the five samples with > 0.5 % m/m Cl and ± 0.19‰ (1s) for the low Cl abundance material (0.27% m/m). We also observed a small, but significant crystal orientation effect of 0.38‰ between the mean ³⁷Cl/³⁵Cl ratios measured on three oriented apatite fragments. Furthermore, the results of GS‐IRMS analyses show small but systematic offset of δ³⁷Cl_SMOC values between the three laboratories. Nonetheless, all studied samples have comparable chlorine isotope compositions, with mean 10³δ³⁷Cl_SMOC values between +0.09 and +0.42 and in all cases with 1s ≤ ± 0.25.     

Denitrification rates measured along a salinity gradient in the eutrophic Neuse River estuary, North Carolina, USA

Denitrification rates along a salinity gradient in the eutrophic Neuse River Estuary, North Carolina, were quantified using membrane inlet mass spectrometry (MIMS) within short-term batch incubations. Denitrification rates within the system were highly variable, ranging from 0 to 275 μmol N m⁻² h⁻¹. Intrasite variability increased with salinity, but no significant differences were observed across the salinity gradient. Denitrification rates were positively correlated with sediment oxygen demand at the upstream sampling site where sediment organic carbon levels were lowest. This relationship was not observed in the more saline sampling sites. Denitrification rates were highest during winter. On an annual basis, denitrification accounted for 26% of the dissolved inorganic nitrogen and 12% of the total nitrogen supplied to the system.     

Phase equilibria in the system CO2-H2O I: New equilibrium relations at low temperatures

Graphical analysis of free-energy relationships involving binary quadruple points and their associated univariant equilibria in the system CO₂-H₂O suggests the presence of at least 2 previously unrecognized quadruple points and a degenerate binary invariant point involving an azeotrope between CO₂-rich gas and liquid. Thermodynamic data extracted from the equilibrium involving clathrate (hydrate), gas, and ice (H = G+I) are employed along with published data to calculate the P-T range of the 3-ice equilibrium curve, S+I = H, where S is solid CO₂. This equilibrium curve intersects the H = G+I curve approximately where the latter curve intersects the S+H = G curve, thus confirming the existence of one of the inferred quadruple points involving the phases S, G, H, and I. Recognition of some binary equilibria probably have been hampered by extremely low mutual solubilities of CO₂ and H₂O in the fluids phases which, for example, render the S+H = G virtually indistinguishable from the CO₂-sublimation curve.To make the published portion of the L(liquid CO₂)-G-H equilibrium “connect” with the other new quadruple point involving S, L, G, and H, it is necessary to change the sense of the equilibrium from L = G+H at higher pressures to L+H = G at lower pressures by positing a L = G azeotrope at very low concentrations of H₂O. At the low-pressure origin of the azeotrope, which is only a few bars above the CO₂-triple point, the azeotrope curve intersects the 3-phase curve tangentially, creating a degenerate invariant point at which the 3-phase equilibrium changes from L+H = G at lower pressures to L = G+H at higher pressures. The azeotrope curve is offset at slightly lower temperature from the L = G+H curve until the 3-phase equilibrium terminates at the quadruple point involving G, L, H, and W (water). With further increase in pressure the azeotrope curve tracks the L = G+W equilibrium and apparently terminates at a critical end point in close proximity to critical endpoints for the CO₂-saturation curve and the L = G+W curve.Thermodynamic data for clathrate extracted from the slope of the H = G+I curve are consistent with a solid-state phase transformation in CO₂-clathrate between 235 and 255 K. Published work shows that the type-I clathrate phase, whose atomic structure is a framework of water molecules with CO₂ molecules situated in large “guest” sites within the framework, is variable in composition with ∼1 guest site vacancy per unit cell at the high-temperature limit of its stability; the number of water molecules, however, remains constant. The formula (CO₂)_8-y·46H₂O, where y is the number of vacancies per unit cell, is in keeping with the atomic structure, whereas the traditional formula, CO₂·nH₂O, where n (hydration number) = 5.75, is misleading.Ambient P-T conditions in the Antarctic and Greenland ice sheets are compatible with sequestering large amounts of carbon as liquid CO₂ and/or clathrate.     

Effects of salinity and temperature on the bioenergetics of adult stages of the grass shrimp (Palaemonetes pugio Holthuis) from the North Inlet Estuary, South Carolina

The influence of temperature, salinity, body size, and sex on the bioenergetics and life-history parameters of grass shrimp (Palaemonetes pugio Holthuis) was determined under laboratory conditions. Sex and/or size show a highly significant effect only on energy allocation for metabolism. Temperature, salinity and their interaction are the main effects on most energetic parameters, with temperature showing the strongest influence on both life-history parameters and energetics. The adult grass shrimp's energy budget is different from that of larval or juvenile stages, in that most of the energy ingested by adults is allocated to reproduction. Under optimal conditions (25°C and 28‰), allocation of ingested energy in the adult grass shrimp is 51.7% for reproduction, 25.4% for respiration, 14.1% for somatic growth, 4.8% for exoskeletons, and 1.8% for excretion.     

Chemical fractionations in meteorites—X. Ureilites

Four ureilites (Dyalpur, Goalpara, Haverö, and Novo Urei) were analyzed by radiochemical neutron activation analysis for Ag, Au, Bi, Br, Cd, Cs, Ge, In, Ir, Ni, Rb, Re, Sb, Se, Te, Tl, and U. An attempt has been made to resolve the data into contributions from the parent ultramafic rock and the injected, carbon- and gas-rich vein material. Interelement correlations, supported by analyses of separated vein material (WANKE et al, 1972), suggest that the vein material is enriched about 10-fold in refractory Ir and Re over moderately volatile Ni and Au, and is low in volatiles except Ge, C, and noble gases. It appears to be a refractory-rich nebular condensate that precipitated carbon by surface catalytic reactions at ˜500K and trapped noble gases but few other volatiles. The closest known analogue is a Cr- and C-rich fraction from the Allende meteorite, highly enriched in heavy noble gases and noble metals. By analogy with Allende, the gas-bearing phase in ureilites may have been an Fe, Cr-sulfide.

The ultramafic rock contains siderophiles and chalcophiles (Ni, Au, Ge, S, Se) at ˜0.05 of Cl chondrite level, and highly volatile elements (Rb, Cs, Bi, Tl, Br, Te, In, Cd) at ˜0.01 Cl level. It probably represents the residue from partial melting of a C3V-like chondrite body, under conditions where phase separation was incomplete so that some liquid was retained. The vein material was injected into this rock at some later time.     

The transformation behaviour of bornite

Phase transformations in bornite have been observed dynamically by in situ experiments in a transmission electron microscope. A series of superstructure phases is formed with decreasing temperature and a new polymorph with a 3a supercell is described. Ordering behaviour with the formation of antiphase domains is proposed as an alternative to the generally accepted twinning mechanism for the transformation to the 2a type.Work carried out while on leave at Department of Mineralogy and Petrology, Cambridge     

Chemical classification of iron meteorites—VIII. Groups IC. IIE,IIIF and 97 other irons

Concentrations of Ni, Ga, Ge and Ir in 106 iron meteorites are reported. Three new groups are defined: IC, IIE and IIIF containing 10, 12 and 5 members, respectively, raising the number of independent groups to 12. Group IC is a cohenite-rich group distantly related to IA. Group IIE consists of those irons previously designated Weekeroo Station type and five others having similar compositions though diverse structures. The IIE irons are compositionally similar to the mesosiderites and pallasites, and the three groups probably formed at similar heliocentric distances. The mixing of the globular IIE silicates with the metal probably occurred during shock events. Group IIIF is a well-defined group of low-Ni and low-Ge irons. The compositions of these groups are summarized as follows:

     

138.

Submarine hydrothermal activity and gold-rich mineralization at Brothers Volcano, Kermadec Arc, New Zealand     

Cornel E. J. de Ronde  Gary J. Massoth  David A. Butterfield  Bruce W. Christenson  Junichiro Ishibashi  Robert G. Ditchburn  Mark D. Hannington  Robert L. Brathwaite  John E. Lupton  Vadim S. Kamenetsky  Ian J. Graham  Georg F. Zellmer  Robert P. Dziak  Robert W. Embley  Vesselin M. Dekov  Frank Munnik  Janine Lahr  Leigh J. Evans  Ken Takai 《Mineralium Deposita》2011,46(5-6):541-584

Brothers volcano, of the Kermadec intraoceanic arc, is host to a hydrothermal system unique among seafloor hydrothermal systems known anywhere in the world. It has two distinct vent fields, known as the NW Caldera and Cone sites, whose geology, permeability, vent fluid compositions, mineralogy, and ore-forming conditions are in stark contrast to each other. The NW Caldera site strikes for ??600?m in a SW?CNE direction with chimneys occurring over a ??145-m depth interval, between ??1,690 and 1,545?m. At least 100 dead and active sulfide chimney spires occur in this field and are typically 2?C3?m in height, with some reaching 6?C7?m. Their ages (at time of sampling) fall broadly into three groups: <4, 23, and 35?years old. The chimneys typically occur near the base of individual fault-controlled benches on the caldera wall, striking in lines orthogonal to the slopes. Rarer are massive sulfide crusts 2?C3?m thick. Two main types of chimney predominate: Cu-rich (up to 28.5?wt.% Cu) and, more commonly, Zn-rich (up to 43.8?wt.% Zn). Geochemical results show that Mo, Bi, Co, Se, Sn, and Au (up to 91?ppm) are correlated with the Cu mineralization, whereas Cd, Hg, Sb, Ag, and As are associated with the dominant Zn-rich mineralization. The Cone site comprises the Upper Cone site atop the summit of the recent (main) dacite cone and the Lower Cone site that straddles the summit of an older, smaller, more degraded dacite cone on the NE flank of the main cone. Huge volumes of diffuse venting are seen at the Lower Cone site, in contrast to venting at both the Upper Cone and NW Caldera sites. Individual vents are marked by low-relief (??0.5?m) mounds comprising predominately native sulfur with bacterial mats. Vent fluids of the NW Caldera field are focused, hot (??300°C), acidic (pH????2.8), metal-rich, and gas-poor. Calculated end-member fluids from NW Caldera vents indicate that phase separation has occurred, with Cl values ranging from 93% to 137% of seawater values. By contrast, vent fluids at the Cone site are diffuse, noticeably cooler (??122°C), more acidic (pH?1.9), metal-poor, and gas-rich. Higher-than-seawater values of SO₄ and Mg in the Cone vent fluids show that these ions are being added to the hydrothermal fluid and are not being depleted via normal water/rock interactions. Iron oxide crusts 3?years in age cover the main cone summit and appear to have formed from Fe-rich brines. Evidence for magmatic contributions to the hydrothermal system at Brothers includes: high concentrations of dissolved CO₂ (e.g., 206?mM/kg at the Cone site); high CO₂/³He; negative ??D and ??¹⁸O_H2O for vent fluids; negative ??³⁴S for sulfides (to ?4.6??), sulfur (to ?10.2??), and ??¹⁵N₂ (to ?3.5??); vent fluid pH values to 1.9; and mineral assemblages common to high-sulfidation systems. Changing physicochemical conditions at the Brothers hydrothermal system, and especially the Cone site, occur over periods of months to hundreds of years, as shown by interlayered Cu?+?Au- and Zn-rich zones in chimneys, variable fluid and isotopic compositions, similar shifts in ³He/⁴He values for both Cone and NW Caldera sites, and overprinting of ??magmatic?? mineral assemblages by water/rock-dominated assemblages. Metals, especially Cu and possibly Au, may be entering the hydrothermal system via the dissolution of metal-rich glasses. They are then transported rapidly up into the system via magmatic volatiles utilizing vertical (??2.5?km long), narrow (??300-m diameter) ??pipes,?? consistent with evidence of vent fluids forming at relatively shallow depths. The NW Caldera and Cone sites are considered to represent stages along a continuum between water/rock- and magmatic/hydrothermal-dominated end-members.     

139.

Drawing the line: the history of the Jurassic—Cretaceous boundary     

John C.W. Cope 《Proceedings of the Geologists' Association. Geologists' Association》2008,119(1):105-117

     

140.

Timescales of partial melting in the Himalayan middle crust: insight from the Leo Pargil dome, northwest India   总被引：5，自引：0，他引：5  

Graham W. Lederer  John M. Cottle  Micah J. Jessup  Jackie M. Langille  Talat Ahmad 《Contributions to Mineralogy and Petrology》2013,166(5):1415-1441

The Leo Pargil dome (LPD) in northwest India exposes an interconnected network of pre-, syn-, and post-kinematic leucogranite dikes and sills that pervasively intrude amphibolite-facies metapelites of the mid-crustal Greater Himalayan sequence. Leucogranite bodies range from thin (5-cm-wide) locally derived sills to thick (2-m-wide) crosscutting dikes extending at least 100 m. Three-dimensional exposures elucidate crosscutting relations between different phases of melt injection and crystallization. Combined laser ablation inductively coupled plasma mass spectrometry U–Th/Pb geochronology and trace element analysis on well-characterized monazite grains from nineteen representative leucogranites yields a large, internally consistent data set of approximately 700 U–Th/Pb and 400 trace element analyses. Grain-scale variations in age correlate with trace element distributions and indicate semi-continuous crystallization of monazite from 30 to 18 Ma. The youngest U–Th/Pb ages in a given sample are consistent with the outcrop-scale crosscutting relations, whereas older ages within individual samples record inheritance from partially crystallized melt and source metapelites. U–Th/Pb isotopic and trace element data are incorporated into a model of melting within the LPD that involves (1) steady-state equilibrium batch melting of compositionally homogeneous metapelitic sources; (2) pulses of increased melt mobility lasting 1–2 m.y. resulting in segregation of melt from its source and amalgamation into mixed magmas; and (3) rapid emplacement and final crystallization of leucogranite bodies. Melt systems in the LPD evolved from locally derived, in situ melt in migmatitic source rocks into a vast network of dikes and sills in the overlying non-migmatitic host rocks.     

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Group	Ni (%)	Ga (ppm)	Ge (ppm)	Ir (ppm)
IC	6.1–6.8	42–54	85–250	0.07–10
IIE	7.5–9.7	21–28	62–75	0.5–8
IIIF	6.8–7.8	6.3–7.2	0.7–1.1	1.3–7.9

Submarine hydrothermal activity and gold-rich mineralization at Brothers Volcano, Kermadec Arc, New Zealand

Brothers volcano, of the Kermadec intraoceanic arc, is host to a hydrothermal system unique among seafloor hydrothermal systems known anywhere in the world. It has two distinct vent fields, known as the NW Caldera and Cone sites, whose geology, permeability, vent fluid compositions, mineralogy, and ore-forming conditions are in stark contrast to each other. The NW Caldera site strikes for ??600?m in a SW?CNE direction with chimneys occurring over a ??145-m depth interval, between ??1,690 and 1,545?m. At least 100 dead and active sulfide chimney spires occur in this field and are typically 2?C3?m in height, with some reaching 6?C7?m. Their ages (at time of sampling) fall broadly into three groups: <4, 23, and 35?years old. The chimneys typically occur near the base of individual fault-controlled benches on the caldera wall, striking in lines orthogonal to the slopes. Rarer are massive sulfide crusts 2?C3?m thick. Two main types of chimney predominate: Cu-rich (up to 28.5?wt.% Cu) and, more commonly, Zn-rich (up to 43.8?wt.% Zn). Geochemical results show that Mo, Bi, Co, Se, Sn, and Au (up to 91?ppm) are correlated with the Cu mineralization, whereas Cd, Hg, Sb, Ag, and As are associated with the dominant Zn-rich mineralization. The Cone site comprises the Upper Cone site atop the summit of the recent (main) dacite cone and the Lower Cone site that straddles the summit of an older, smaller, more degraded dacite cone on the NE flank of the main cone. Huge volumes of diffuse venting are seen at the Lower Cone site, in contrast to venting at both the Upper Cone and NW Caldera sites. Individual vents are marked by low-relief (??0.5?m) mounds comprising predominately native sulfur with bacterial mats. Vent fluids of the NW Caldera field are focused, hot (??300°C), acidic (pH????2.8), metal-rich, and gas-poor. Calculated end-member fluids from NW Caldera vents indicate that phase separation has occurred, with Cl values ranging from 93% to 137% of seawater values. By contrast, vent fluids at the Cone site are diffuse, noticeably cooler (??122°C), more acidic (pH?1.9), metal-poor, and gas-rich. Higher-than-seawater values of SO₄ and Mg in the Cone vent fluids show that these ions are being added to the hydrothermal fluid and are not being depleted via normal water/rock interactions. Iron oxide crusts 3?years in age cover the main cone summit and appear to have formed from Fe-rich brines. Evidence for magmatic contributions to the hydrothermal system at Brothers includes: high concentrations of dissolved CO₂ (e.g., 206?mM/kg at the Cone site); high CO₂/³He; negative ??D and ??¹⁸O_H2O for vent fluids; negative ??³⁴S for sulfides (to ?4.6??), sulfur (to ?10.2??), and ??¹⁵N₂ (to ?3.5??); vent fluid pH values to 1.9; and mineral assemblages common to high-sulfidation systems. Changing physicochemical conditions at the Brothers hydrothermal system, and especially the Cone site, occur over periods of months to hundreds of years, as shown by interlayered Cu?+?Au- and Zn-rich zones in chimneys, variable fluid and isotopic compositions, similar shifts in ³He/⁴He values for both Cone and NW Caldera sites, and overprinting of ??magmatic?? mineral assemblages by water/rock-dominated assemblages. Metals, especially Cu and possibly Au, may be entering the hydrothermal system via the dissolution of metal-rich glasses. They are then transported rapidly up into the system via magmatic volatiles utilizing vertical (??2.5?km long), narrow (??300-m diameter) ??pipes,?? consistent with evidence of vent fluids forming at relatively shallow depths. The NW Caldera and Cone sites are considered to represent stages along a continuum between water/rock- and magmatic/hydrothermal-dominated end-members.     

Timescales of partial melting in the Himalayan middle crust: insight from the Leo Pargil dome, northwest India

The Leo Pargil dome (LPD) in northwest India exposes an interconnected network of pre-, syn-, and post-kinematic leucogranite dikes and sills that pervasively intrude amphibolite-facies metapelites of the mid-crustal Greater Himalayan sequence. Leucogranite bodies range from thin (5-cm-wide) locally derived sills to thick (2-m-wide) crosscutting dikes extending at least 100 m. Three-dimensional exposures elucidate crosscutting relations between different phases of melt injection and crystallization. Combined laser ablation inductively coupled plasma mass spectrometry U–Th/Pb geochronology and trace element analysis on well-characterized monazite grains from nineteen representative leucogranites yields a large, internally consistent data set of approximately 700 U–Th/Pb and 400 trace element analyses. Grain-scale variations in age correlate with trace element distributions and indicate semi-continuous crystallization of monazite from 30 to 18 Ma. The youngest U–Th/Pb ages in a given sample are consistent with the outcrop-scale crosscutting relations, whereas older ages within individual samples record inheritance from partially crystallized melt and source metapelites. U–Th/Pb isotopic and trace element data are incorporated into a model of melting within the LPD that involves (1) steady-state equilibrium batch melting of compositionally homogeneous metapelitic sources; (2) pulses of increased melt mobility lasting 1–2 m.y. resulting in segregation of melt from its source and amalgamation into mixed magmas; and (3) rapid emplacement and final crystallization of leucogranite bodies. Melt systems in the LPD evolved from locally derived, in situ melt in migmatitic source rocks into a vast network of dikes and sills in the overlying non-migmatitic host rocks.