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Processes and kinetics of Cd2+ sorption by a calcareous aquifer sand

The rate of Cd2+ sorption by a calcareous aquifer sand was characterized by two reaction steps, with the first step reaching completion in 24 hours. The second step proceeded at a slow and nearly constant rate for at least seven days. The first step includes a fast adsorption reaction which is followed by diffusive transport into either a disordered surface film of hydrated calcium carbonate or into pore spaces. After 24 hours the rate of Cd2+ sorption was constant and controlled by the rate of surface coprecipitation, as a solid solution of CdCO3 in CaCO3 formed in recrystallizing material. Desorption of Cd2+ from the sand was slow. Clean grains of primary minerals, e.g. quartz and aluminosilicates. sorbed much less Cd2+ than grains which had surface patches of secondary minerals, e.g. carbonates, iron and manganese oxides. Calcite grains sorbed the greatest amount of Cd2+ on a weight-normalized basis despite the greater abundance of quartz. A method is illustrated for determining empirical binding constants for trace metals at in situ pH values without introducing the experimental problem of supersaturation. The binding constants are useful for solute transport models which include a computation of aqueous speciation.

Geochimica et Cosmochimica Acta

Synthesis and stability of hetaerolite, ZnMn2O4, at 25°C

A precipitate of nearly pure hetaerolite, ZnMn 2 O 4 , a spinel-structured analog of hausmannite, Mn 3 O 4 , was prepared by an irreversible wprecipitation of zinc with manganese at 25°C. The synthesis technique entailed constant slow addition of a dilute solution of Mn 2+ and Zn 2+ chlorides having a Mn/Zn ratio of 2:1 to a reaction vessel that initially contained distilled deionized water, maintained at a pH of 8.50 by addition of dilute NaOH by an automated pH stat, with continuous bubbling of CO 2 -free air. The solid was identified by means of X-ray diffraction and transmission electron microscopy and consisted of bipyramidal crystals generally less than 0.10 μm in diameter. Zn 2+ ions are able to substitute extensively for Mn 2+ ions that occupy tetrahedral sites in the hausmannite structure. Hetaerolite appears to be more stable than hausmannite with respect to spontaneous conversion to γMnOOH. The value of the standard free energy of formation of hetaerolite was estimated from the experimental data to be −289.4 ± 0.8 kcal per mole. Solids intermediate in composition between hetaerolite and hausmannite can be prepared by altering the Mn/Zn ratio in the feed solution.

Geochimica et Cosmochimica Acta

Aqueous pyrite oxidation by dissolved oxygen and by ferric iron

Rates of aqueous, abiotic pyrite oxidation were measured in oxygen-saturated and anaerobic Fe(III)-saturated solutions with initial pH from 2 to 9. These studies included analyses of sulfite, thiosulfate, polythionates and sulfate and procedures for cleaning oxidation products from pyrite surfaces were evaluated. Pyrite oxidation in oxygen-saturated solutions produced (1) rates that were only slightly dependent on initial pH, (2) linear increases in sulfoxy anions and (3) thiosulfate and polythionates at pH > 3.9. Intermediate sulfoxy anions were observed only at high stirring rates. In anaerobic Fe(III)-saturated solutions, no intermediates were observed except traces of sulfite at pH 9. The faster rate of oxidation in Fe(III)-saturated solutions supports a reaction mechanism in which Fe(III) is the direct oxidant of pyrite in both aerobic and anaerobic systems. The proposal of this mechanism is also supported by theoretical considerations regarding the low probability of a direct reaction between paramagnetic molecular oxygen and diamagnetic pyrite. Results from a study of sphalerite oxidation support the hypothesis that thiosulfate is a key intermediate in sulfate production, regardless of the bonding structure of the sulfide mineral.

Geochimica et Cosmochimica Acta

Sources and flux of natural gases from Mono Lake, California

The ability to identify a formation mechanism for natural gas in a particular environment requires consideration of several geochemical factors when there are multiple sources present. Four primary sources of methane have been identified in Mono Lake. Two of these sources were associated with numerous natural gas seeps which occur at various locations in the lake and extend beyond its present boundary; the two other gas sources result from current microbiological processes. In the natural gas seeps, we observed flow rates as high as 160 moles CH 4 day −1 , and estimate total lakewide annual seep flux to be 2.1 × 10 6 moles CH 4 . Geochemical parameters ( δ 13 CH 4 , δDCH 4 , CH 4 /[ C 2 H 6 + C 3 H 8 ]) and δ 14 CH 4 measurements revealed that most of the seeps originate from a paleo-biogenic ( δ 13 CH 4 = about −70%.). natural gas deposit of Pleistocene age which underlies the current and former lakebed. Gas seeps in the vicinity of hot springs had, in combination with the biogenic gas, a prominent thermogenic gas component resulting from hydrothermal alteration of buried organic matter.

California

Compositional evidence regarding the origins of rims on Semarkona chondrules

The compositions of the interiors and abraded surfaces of 7 chondrules from Semarkona (LL3.0) were measured by neutron activation analysis. For nonvolatile elements, the lithophile and siderophile element abundance patterns in the surfaces are generally similar to those in the corresponding interiors. Siderophile and chalcophile concentrations are much higher in the surfaces, whereas lithophile concentrations are similar in both fractions. Most of the similarities in lithophile patterns and some of the similarities in siderophile patterns between surfaces and interiors may reflect incomplete separation of the fractions in the laboratory, but for 3 or 4 chondrules the siderophile resemblance is inherent, implying that the surface and interior metal formed from a single precursor assemblage. Metal and sulfide-rich chondrule rims probably formed when droplets of these phases that migrated to the chondrule surface during melting were reheated and incorporated into matrix-like material that had accreted onto the surface. The moderately-volatile to volatile elements K, As and Zn tend to be enriched in the surfaces compared with other elements of similar mineral affinity; both enrichments and depletions are observed for other moderately volatile elements. A small fraction of chondrules experienced fractional evaporation while they were molten.

Geochimica et Cosmochimica Acta

Bacterial ethane formation from reduced, ethylated sulfur compounds in anoxic sediments

Trace levels of ethane were produced biologically in anoxic sediment slurries from five chemically different aquatic environments. Gases from these locations displayed biogenic characteristics, having 12 C-enriched values of δ 13 CH 4 (−62 to −86%.), δ 13 C 2 H 6 (−35 to −55%.) and high ratios (720 to 140,000) of CH 4 [C 2 H 6 + C 3 H 8 ] "> CH4[C2H6+ C3H8] . Endogenous production of ethane by slurries was inhibited by autoclaving or by addition of the inhibitor of methanogenic bacteria, 2-bromoethanesulfonic acid (BES). Ethane formation was stimulated markedly by ethanethiol (ESH), and, to a lesser extent, by diethylsulfide (DES). Formation of methane and ethane in ESH- or DES-amended slurries was blocked by BES. Experiments showed that ethionine (or an analogous compound) could be a precursor of ESH. Ethylamine or ethanol additions to slurries caused only a minor stimulation of ethane formation. Similarly, propanethiol additions resulted in only a minor enhancement of propane formation. Cell suspensions of a methyltrophic methanogen produced traces of ethane when incubated in the presence of DES, although the organism did not grow on this compound. These results indicate that methanogenic bacteria produce ethane from the traces of ethylated sulfur compounds present in recent sediments. Preliminary estimates of stable carbon isotope fractionation associated with sediment methane formation from dimethylsulfide was about 40%., while ethane formation from DES and ESH was only 4. 6 and 6.5%., respectively.

Geochimica et Cosmochimica Acta

Isotopic evidence for organic matter oxidation by manganese reduction in the formation of stratiform manganese carbonate ore

Unlike other marine-sedimentary manganese ore deposits, which are largely composed of manganese oxides, the primary ore at Molango (Hidalgo State, Mexico) is exclusively manganese carbonate (rhodochrosite, Mn-calcite, kutnahorite). Stable isotope studies of the carbonates from Molango provide critical new information relevant to the controversy over syngenetic and diagenetic models of stratiform manganese deposit formation. Negative δ 13 C values for carbonates from mineralized zones at Molango are strongly correlated with manganese content both on a whole rock scale and by mineral species. Whole rock δ 13 C data fall into three groups: high-grade ore = −16.4 to −11.5%.; manganese-rich, sub-ore-grade = −5.2 to 0%.; and unmineralized carbonates = 0 to +2.5%. (PDB). δ 18 O data show considerable overlap in values among the three groups: +4.8 to −2.8, −5.4 to −0.3%., and −7.4 to +6.2 (PDB), respectively. Isotopic data for individual co-existing minerals suggest a similar separation of δ 13 C values: δ 13 C values from calcite range from −1.1 to +0.7%. (PDB), whereas values from rhodochrosite are very negative, −12.9 to −5.5%., and values from kutnahorite or Mn-calcite are intermediate between calcite and rhodochrosite. 13 C data are interpreted to indicate that calcite ( i.e . unmineralized carbonate) formed from a normal marine carbon reservoir. However, 13 C data for the manganese-bearing carbonates suggest a mixed seawater and organic source of carbon. The presence of only trace amounts of pyrite suggests sulfate reduction may have played a minor part in oxidizing organic matter. It is possible that manganese reduction was the predominant reaction that oxidized organic matter and that it released organic-derived CO 2 to produce negative δ 13 C values and manganese carbonate mineralization.

Geochimica et Cosmochimica Acta

Hydrogen concentrations as an indicator of the predominant terminal electron-accepting reactions in aquatic sediments

Factors controlling the concentration of dissolved hydrogen gas in anaerobic sedimentary environments were investigated. Results, presented here or previously, demonstrated that, in sediments, only microorganisms catalyze the oxidation of H2 coupled to the reduction of nitrate, Mn(IV), Fe(III), sulfate, or carbon dioxide. Theoretical considerations suggested that, at steady-state conditions, H2 concentrations are primarily dependent upon the physiological characteristics of the microorganism(s) consuming the H2 and that organisms catalyzing H2 oxidation, with the reduction of a more electrochemically positive electron acceptor, can maintain lower H2 concentrations than organisms using electron acceptors which yield less energy from H2 oxidation. The H2 concentrations associated with the specified predominant terminal electron-accepting reactions in bottom sediments of a variety of surface water environments were: methanogenesis, 7-10 nM; sulfate reduction, 1-1.5 nM; Fe(III) reduction, 0.2 nM; Mn(IV) or nitrate reduction, less than 0.05 nM. Sediments with the same terminal electron acceptor for organic matter oxidation had comparable H2 concentrations, despite variations in the rate of organic matter decomposition, pH, and salinity. Thus, each terminal electron-accepting reaction had a unique range of steady-state H2 concentrations associated with it. Preliminary studies in a coastal plain aquifer indicated that H2 concentrations also vary in response to changes in the predominant terminal electron-accepting process in deep subsurface environments. These studies suggest that H2 measurements may aid in determining which terminal electron-accepting reactions are taking place in surface and subsurface sedimentary environments.

Geochimica et Cosmochimica Acta

Liquid-vapor relations in the critical region of the system NaCl-H 2 O from 380 to 415°C: A refined determination of the critical point and two-phase boundary of seawater

Pressure-temperature-composition ( P - T - x ) relations for coexisting vapor and liquid phases in the system NaCl-H 2 O were determined experimentally in the critical region from 380 to 415°C. The results provide much improved control on the P - T - x critical line in this region. The critical point of seawater (3.2 wt% NaCl solution), which is bracketed in the present study, is at 407°C and 298.5 bar. In addition, the P - T two-phase boundary of seawater was re-determined. These results provide increased precision and accuracy for theoretical models of critical phenomena in this important two-component system and of the limiting P - T conditions of seawater in seafloor geothermal systems.

Geochimica et Cosmochimica Acta

The metal oxide fraction of pelagic sediment in the equatorial North Pacific Ocean: A source of metals in ferromanganese nodules

Pelagic sediment recovered at DOMES Site A in the equatorial North Pacific (151°W, 9° 15′N) consists of a surface homogeneous layer, approximately 10 cm thick, overlying a strongly mottled layer that is lighter in color. The radiolarian composition of both units is Quaternary. In areas where this sediment was only a few centimeters thick, the underlying sediment was early Tertiary. Clay mineralogy and major oxide composition of the two Quaternary sediments are uniform. Their similarity to continental shale suggests that the sediment has a terrigenous source. Clay mineralogy and major oxide composition of the Tertiary sediment also are uniform, although they differ markedly from the Quarternary sediment. In contrast to the major oxides, concentrations of Mn, Co, Cu, and Ni soluble in hydroxylamine hydrochlorideacetic acid are strongly different in the surface and subsurface Quaternary sediment. Mn and Ni exhibit pronounced depletions in the subsurface sediment, Ni slightly more than Mn. Cu is also depleted in the subsurface sediment, but less than Mn. It is also depleted in the subsurface Tertiary sediment, whereas the Mn concentration remains high. Concentration of Co relative to Mn increases into the subsurface Quaternary sediment to a constant Co:Mn ratio of 3 × 10 −2 . The trivalent REE (the REE exclusive of Ce) and Fe exhibit little down-core variation. Distribution of elements in these sediments is closely related to their concentration in associated surface ferromanganese nodules. The nodules are of two distinct types: those from the area where the Quaternary sediment is relatively thick have δ-MnO 2 as the dominant manganese mineral. The ratios of Ni:Mn, Cu:Mn, and Fe:Mn in these nodules approximate the corresponding ratios of the soluble fraction of surface sediment. Todorokite is the dominant mineral of nodules recovered from areas where the Quaternary sediment is thin. Relatively high Cu/Mn, Ni/Mn, and low Fe/Mn ratios of these nodules mirror differences between the soluble fraction of surface and subsurface Quaternary sediment. These compositional trends of sediment and nodules at DOMES Site A reflect a diagenetic origin for the todorokite nodules and a predominantly hydrogenous origin for the δ-MnO 2 nodules.

Geochimica et Cosmochimica Acta

The plumbotectonic model for Pb isotopic systematics among major terrestrial reservoirs: A case for bi-directional transport

Version IV of plumbotectonics expands and refines the original model of Doe and Zartman (1979) and Zartman and Doe (1981) for explaining Pb (Sr, and Nd) isotopic systematics among major terrestrial reservoirs. A case for bi-directional transport among reservoirs is based on the observed isotopic compositions for different tectonic settings, and finds a rationale in the kinetics of plate tectonics. Chemical fractionation and radioactive decay create isotopic differences during periods of isolation of one reservoir from another, whereas dynamic processes allowing mixing between reservoirs tend to reduce these differences. Observed isotopic characteristics reflect a balance between these opposing tendencies and provide constraints on the extent and timing of fractionation and mixing processes. Plumbotectonics does not require interaction with a lower mantle or core reservoir over most of the Earth's lifetime, and, in fact, achieves a material balance consistent with no such exchange of material. Important evidence of the amount and timing of crustal recycling, and of the residence times of mantle heterogeneities lies in the coupled 207 Pb 204 Pb- 206 Pb 204 Pb "> 207 Pb 204 Pb- 206 Pb 204 Pb systematics. We believe that examination of the published data base fully supports our contention of significant bi-directional transport of material among terrestrial reservoirs. Plumbotectonics allows us to explore many aspects of reservoir interaction, and to identify parameters that provide meaningful constraints on mantle-crust differentiation. We put forth a compromise fit to many of the model variables in version IV, which can serve as a reference for future work.

Geochimica et Cosmochimica Acta

High-resolution 40Ar 39Ar chronology of Oligocene volcanic rocks, San Juan Mountains, Colorado

The central San Juan caldera complex consists of seven calderas from which eight major ash-flow tuffs were erupted during a period of intense volcanic activity that lasted for approximately 2 m.y. about 26–28 Ma. The analytical precision of conventional K-Ar dating in this time interval is not sufficient to unambiguously resolve this complex history. However, 40 Ar 39 Ar "> 40 Ar 39 Ar incremental-heating experiments provide data for a high-resolution chronology that is consistent with stratigraphie relations. Weighted-mean age-spectrum plateau ages of biotite and sanidine are the most precise with standard deviations ranging from 0.08 to 0.21 m.y. The pooled estimate of standard deviation for the plateau ages of 12 minerals is about 0.5 percent or about 125,000 to 135,000 years. Age measurements on coexisting minerals from one tuff and on two samples of each of two other tuffs indicate that a precision in the age of a tuff of better than 100,000 years can be achieved at 27 Ma. New data indicate that the San Luis caldera is the youngest caldera in the central complex, not the Creede caldera as previously thought.

Geochimica et Cosmochimica Acta

The dissolution of quartz in dilute aqueous solutions of organic acids at 25°C

The dissolution of quartz in dilute aqueous solutions of organic acids at 25° and standard pressure was investigated by the batch dissolution method. The bulk dissolution rate of quartz in 20 mmole/Kg citrate solutions at pH 7 was 8 to 10 times faster than that in pure water. After 1750 hours the concentration of dissolved silica in the citrate solution was 167 μmole/Kg compared to 50 μmole/Kg in water and a 20 mmole/Kg solution of acetate at pH 7. Solutions of salicylic, oxalic, and humic acids also accelerated the dissolution of quartz in aqueous solution at pH 7. The rate of dissolution in organic acids decreased sharply with decreasing pH. The possibility of a silica-organic acid complex was investigated using UV-difference spectroscopy. Results suggest that dissolved silica is complexed by citrate, oxalate and pyruvate at pH 7 by an electron-donor acceptor complex, whereas no complexation occurs between silica and acetate, lactate, malonate, or succinate. Three models are proposed for the solution and surface complexation of silica by organic acid anions which result in the accelerated dissolution and increased solubility of quartz in organic rich water.

Geochimica et Cosmochimica Acta

Fluid inclusions in vadose cement with consistent vapor to liquid ratios, Pleistocene Miami Limestone, southeastern Florida

Vadose cements in the Late Pleistocene Miami Limestone contain regions with two-phase aqueous fluid inclusions that have consistent vapor to liquid (V-L) ratios. When heated, these seemingly primary inclusions homogenize to a liquid phase in a range between 75°C and 130°C (mean = 100° C ) and have final melting temperatures between −0.3° and 0.0°C. The original distribution of T h was broadened during measurements because of fluid inclusion reequilibration. The narrow range of T h in these fluid inclusions suggest unusually consistent V-L ratios. They occur with small, obscure, single phase liquid-filled inclusions, which infer a low temperature origin (less than 60°C), and contradict the higher temperature origin implied by the two phase inclusions. The diagenetic environment producing these seemingly primary fluid inclusions can be inferred from the origin of the host calcite enclosing them. The δ 18 O composition of these cements (−4 to−5.5%., PDB) and the fresh water in the fluid inclusions are consistent with precipitation from low-temperature meteoric water. The carbon-isotope composition of the vadose cements that contain only rare two-phase fluid inclusions are comparable to the host rock matrix (δ 13 C between 0 and +4%., PDB). Cements that contain common two-phase fluid-inclusions have a distinctly lighter carbon isotopic composition of −3 to −5%.. The carbon isotope composition of cements that contain common two-phase inclusions are about 6%. lighter than those of other vadose cements; models of early meteoric diagenesis indicate that this is the result of precipitation from water that has been influenced by soil gas CO 2 . Our hypothesis is that the primary fluid inclusions, those with consistent V-L ratios and the single-phase liquid inclusions, form at near-surface temperature (25°C) and pressure when consistent proportions of soil gas and meteoric water percolating through the vadose zone are trapped within elongate vacuoles. This study corroborates that T h measurements on two phase inclusions in vadose cements can be misleading evidence of thermal diagenesis, even if the measurements are well grouped.

Geochimica et Cosmochimica Acta

Experimental oxygen isotope fractionation between siderite-water and phosphoric acid liberated CO2-siderite

The equilibrium fractionation of O isotopes between synthetic siderite and water has been measured at temperatures ranging from 33° to 197°C. The fractionation between siderite and water over this temperature range can be represented by the equation: 10 3 ln α = 3.13 × 10 6 T −2 − 3.50. Comparison between the experimental and theoretical fractionations is favorable only at approximately 200°C; at lower temperatures, they generally differ by up to 2 permil. Siderite was prepared by the slow addition of ferrous chloride solutions to sodium bicarbonate solutions at the experimental temperatures. It was also used to determine the O isotope fractionation factors between phosphoric acid liberated CO 2 and siderite. The fractionation factors for this pair at 25° and 50°C are 1.01175 and 1.01075, respectively. Preliminary results of the measured C isotope fractionation between siderite and Co 2 also indicate C isotopic equilibrium during precipitation of siderite. The measured distribution of 13 C between siderite and CO 2 coincides with the theoretical values only at about 120°C. Experimental and theoretical C fractionations differ up to 3 permil at higher and lower temperatures.

Geochimica et Cosmochimica Acta

River Valley pluton, Ontario: A late-Archean/early-Proterozoic anorthositic intrusion in the Grenville Province

The River Valley pluton is a ca . 100 km 2 body of anorthositic and gabbroic rocks located about 50 km northeast of Sudbury, Ontario. The pluton is situated entirely within the Grenville Province, but its western margin is a series of imbricate thrust faults associated with the Grenville Front Tectonic Zone. It is dominated by coarse leuconorite and leucogabbro, with lesser anorthosite, gabbro, and rare ultramafics. Igneous textured rocks are abundant and consist of plagioclase (An 60–70 ) charged with Fe-Ti oxide inclusions, low Ca pyroxene (orthopyroxene and/or inverted pigeonite) and augite. The most unfractionated rocks are minor olivine gabbros with Fo 70–80 . A variety of deformed and recrystallized equivalents of the igneous-textured rocks is also present, and these are composed largely of calcic plagioclase and hornblende. Ten samples, including both igneous and deformed lithologies give a Pb-Pb whole-rock isochron of 2560±155Ma, which is our best estimate of the time of primary crystallization. The River Valley pluton is thus the oldest anorthositic intrusive yet reported from the Grenville Province, but is more calcic and augitic than typical massifs, and lacks their characteristic Fe-Ti oxide ore deposits. The River Valley body may be more akin to similar gabbro-anorthosite bodies situated at the boundary between the Archean Superior Province and Huronian supracrustal belt of the Southern Province west of the Grenville Front. An Sm-Nd isochron from 3 igneous-textured leucogabbros and an augite mineral separate gives 2377 ± 68 Ma, implying slight disturbance of the Sm-Nd whole-rock-mineral system during later metamorphism. The Rb-Sr system has been substantially disturbed, giving an age of 2185 ± 105 Ma, which is similar to internal Pb-Pb isochron ages of 2165 ± 130 Ma and 2100 ± 35 Ma for two igneous-textured rocks. It is uncertain whether these ages correspond to a discrete event at this time or represent a partial resetting of the Rb-Sr and Pb-Pb systems from a younger event such as the Grenvillian orogeny of ca . 1.0 Ga. None of the isotopic systems we investigated, however, gives an age near 1.0 Ga, suggesting that neither the River Valley pluton, nor the immediately surrounding gneisses were strongly affected by metamorphism associated with the Grenvillian orogeny. Initial isotopic ratios for the River Valley pluton correspond to single-stage model parameters of μ = 8.06, ϵ Nd = 0 to −3, and I Sr = 0.7015 to 0.7021. Collectively, these suggest either an enriched mantle source or crustal contamination of a mantle-derived magma. The crustal component involved must have been older and more radiogenic than the majority of rocks exposed at the surface in the nearby Superior Province.

Geochimica et Cosmochimica Acta

Enrichment of trace elements in garnet amphibolites from a paleo-subduction zone: Catalina Schist, southern California

The abundance, P - T stability, solubility, and element-partitioning behavior of minerals such as rutile, garnet, sphene, apatite, zircon, zoisite, and allanite are critical variables in models for mass transfer from the slab to the mantle wedge in deep regions of subduction zones. The influence of these minerals on the composition of subduction-related magmas has been inferred (and disputed) from inverse modelling of the geochemistry of island-arc basalt, or by experiment. Although direct samples of the dehydration + partial-melting region of a mature subduction zone have not been reported from subduction complexes, garnet amphibolites from melanges of circumpacific and Caribbean blueschist terranes reflect high T (>600°C) conditions in shallower regions. Such rocks record geochemical processes that affected deep-seated, high- T portions of paleo-subduction zones. In the Catalina Schist, a subduction-zone metamorphic terrane of southern California, metasomatized and migmatitic garnet amphibolites occur as blocks in a matrix of meta-ultramafic rocks. This mafic and ultramafic complex may represent either slab-derived material accreted to the mantle wedge of a nascent subduction zone or a portion of a shear zone closely related to the slab-mantle wedge contact, or both. The trace-element geochemistry of the complex and the distribution of trace elements among the minerals of garnet amphibolites were studied by INAA, XRF, electron microprobe, and SEM. In order of increasing alteration from a probable metabasalt protolith, three common types of garnet amphibolite blocks in the Catalina Schist are: (1) non-migmatitic, clinopyroxene-bearing blocks, which are compositionally similar to MORB that has lost an albite component; (2) garnet-amphibolite blocks, which have rinds that reflect local interaction between metabasite, metaperidotite, and fluid; and (3) migmatites that are extremely enriched in Th, HFSE, LREE, and other trace elements. These trace-element enrichments are mineralogically controlled by rutile, garnet, sphene, apatite, zircon, zoisite, and allanite. Alkali and alkaline earth elements are much less enriched in the solid assemblage, and thus appear to be decoupled from the other elements in the inferred metasomatic process(es). The compositions of migmatitic garnet amphibolite blocks seem to complement that of “average” island-arc tholeiite. Trace-element metasomatism reflects fluid-solid, rather than melt-solid, interaction. The metasomatic effects indicate that H 2 O-rich fluid, perhaps with a significant component of Na-Al silicate and alkalis, carried Th, U, Sr, REE, and HFSE. Fractionations of LREE in migmatites resemble those of migmatitic metasedimentary rocks underlying the mafic and ultramafic complex. “Exotic” LREE deposited in allanite in migmatites could have been derived from fluids in equilibrium with subducted sediment. If the paleo-subduction zone represented by the mafic and ultramafic complex of the Catalina Schist had continued its thermal and fluid evolution, a selvage of similarly enriched rocks might have been generated along the slab-mantle wedge contact between ~30 and 85 km depth. Rocks affected by “subduction-zone metasomatism,” although rarely recognized at the surface, could be volumetrically significant products of the initiation of subduction and may prove to be geochemical probes of convergent margins that approach the significance of xenoliths in the study of other magmatic environments.

Geochimica et Cosmochimica Acta