Petrology of the Proterozoic Potato River Layered Intrusion, Northern Wisconsin, USA

The Potato River intrusion is a Keweenawan (1100 Ma) mafic plutonemplaced in Keweenawan volcanics and earlier Proterozoic metasedimentaryrocks along the southeastern flank of the Lake Superior syncline.It comprises the following lithostratigraphic zones: a thinto absent Border zone of altered olivine gabbro; a Lower zoneof olivine gabbro; a Picritic zone of picrite and troctolite;a Middle zone of olivine gabbro and leucogabbro; an Upper zoneof quartz leucogabbro and ferrogabbro; and a Roof zone of granophyricand granitic rocks. Fractional crystallization is evident fromcompositional changes in the rocks and cumulus minerals withstratigraphic height. Elements concentrated in the cumulus mineralsolivine and plagioclase (Mg, Fe²⁺, Al, Ca, Ni, Co, Cr, Sr) decreasewith height; elements concentrated in the trapped liquid (Na,K, La, Y, Zr, Nb, Rb, Ba) increase with height; and other elements(Ti, Fe³⁺, P, Ga, V, Sc, Cu, Zn) show complicated behavior relatedto the appearance of additional cumulus phases such as clinopyroxene,Fe-Ti oxides, and apatite. Lower zone rocks contain some sulfide,probably from sulfur derived from the country rock, and theUpper zone has sulfides probably precipitated from an immisciblesulfide liquid. The sulfide-bearing rocks have similaritiesto those of other intrusions, such as Bushveld, Stillwater,and Skaergaard. The picritic and troctolitic rocks of the Picritic zone indicatethat the intrusion was open to additional injections of maficmagma. Roof zone granophyric rocks are residual liquids intrudedalong the upper margin of the intrusion during regional tilting,but Roof zone granitic rocks are probably melted country rock.An attempt is made to estimate by reverse stratigraphic summationthe compositional path of the magma that solidified above thePicritic zone. The first compositions are highly aluminous,which suggests that the upper part of the intrusion has beenenriched in plagioclase by convection-aided crystal sorting.A complementary unit of mafic rocks is not exposed, but it couldbe present down dip. Some of the later compositions are similarto typical Keweenawan high-Al tholeiites. The magma did notundergo extreme iron enrichment, probably because of oxygenfugacity buffering.     

Experimental study of igneous and sedimentary apatite dissolution: Control of pH, distance from equilibrium, and temperature on dissolution rates

Apatite dissolution experiments were conducted using both a fluidized bed and stirred tank reactor over a range of pH, temperature, solution saturation state, and on non-carbonated and carbonated apatite compositions: igneous fluorapatite (FAP) and sedimentary carbonate fluorapatite (CFA), respectively. From 2 <pH <6, the rate of release from dissolution of all apatite components [calcium (Ca), phosphorus (P), and fluoride (F)] increased with decreasing pH for FAP. From 6 < pH < 8.5, the FAP dissolution rate is pH independent. Measuring apatite dissolution rates at pH > 8.5 were not possible due to detection limits of the analytical techniques used in this study and the high insolubility of FAP. For the CFA compositions studied, the dissolution rate decreased with increasing pH from 4 < pH < 7. During early stages of the dissolution reaction for both FAP and CFA, mineral components were released in non-stoichiometric ratios with reacted solution ratios of dissolved Ca:P and Ca:F being greater than mineral stoichiometric ratios, suggesting that Ca was preferentially released compared to P and F from the mineral structure during the early stages of dissolution. An increase in reacted solution pH accompanies this early elevated release of Ca. As the dissolution reaction proceeded to steady state, dissolution became congruent. When normalized to BET measured surface area, FAP dissolved faster from 4 < pH < 7 compared to CFA. The apparent Arrhenius activation energy (E_a) of FAP dissolution over the temperature range of 25-55°C at pH = 3.0, I = 0.1, and pCO₂ = 0 is 8.3 ± 0.2 kcal mol⁻¹. Both the apparent exchange of solution H⁺ for solid-bound Ca at low pH in the early stage of dissolution and the E_a of dissolution suggest a surface and not a diffusion controlled dissolution reaction for FAP and CFA. The degree of undersaturation of the solution, ΔG_R, with respect to FAP was important in determining the dissolution rate. At pH = 3.0, I = 0.1, and pCO₂ = 0, the dissolution rate of FAP was ∼ 5× greater in the far-from-equilibrium region compared to the near-equilibrium slope region.A simple apatite weathering model incorporating the experimental results from this study was constructed, and numerical calculations suggest that during the Phanerozoic both the surface area of igneous rock available for weathering and the average global temperature were important factors in determining the P weathering flux from apatite dissolution. It is possible that elevated global temperatures coupled with relatively high surface area of igneous rock during the early- to mid-Paleozoic resulted in elevated P weathering fluxes, which along with climatic evolutionary pressures of the Neoproterozoic, facilitated the radiation of multicellular organisms, large-scale phosphorite deposition, and abundance of calcium phosphate shelled organisms during the early Cambrian.     

Fluxes of organic carbon in Manukau Harbour, New Zealand

We collated information on the sources and sinks of organic carbon in Manukau Harbour, a shallow temperate estuary. Two contrasting inner harbor regions were considered; the northern region, which is urbanized and receives a major load of sewage wastewater, and the southern region, where allochthonous inputs are dominated by the runoff from small rural streams. Although high levels of dissolved nitrogen in the wastewater supported phytoplankton blooms in the northern region, total primary production there was similar to that in the southern region (ca. 300 g C m^?2yr^?1). By contrast, high concentrations of organic carbon in the wastewater resulted in an additional input to the northern region of 120 g C m^?2 yr^?1. Loads from runoff and streams to both regions were low. At 350 g C m^?2 yr^?1, total respiration in the northern region exceeded total production, so the region was slightly heterotrophic. Respiration was lower in the southern region (270 g C m^?2 yr^?1), which was net autotrophic. Some carbon was exported from each region to the outer harbour (50–80 g C m^?2 yr^?1). Dissolved oxygen levels in the northern region were somewhat depleted at times; and the high numbers of microzooplankton indicated consumption was enhanced there. Apart from a relatively small area of organic enrichment close to the wastewater discharge, benthic consumers in the harbor appeared to be limited by physical disturbance (by wind-waves) rather than by food availability. Improved wastewater treatment is expected to substantially reduce the allochthonous input to the northern region, with the total input of carbon in the future being only slightly higher than that to the southern region.     

Sr-gorceixite,a weathering product in rich iron ores from the Córrego do Feijão Mine,Minas Gerais,Brazil

A sulfate-bearing Sr-Ba phosphate (Sr-gorceixite) formed by supergene alteration in rich iron ores from Minas Gerais, Brazil, has been studied by means of microprobe techniques. Analytical data and the structural formula are presented.     

Heavy metal and sulfur transport during subcritical and supercritical hydrothermal alteration of basalt: Influence of fluid pressure and basalt composition and crystallinity

Crystalline basalt, diabase and basalt glass have been reacted with a Na-Ca-K-Cl fluid of seawater ionic strength at 350–425°C, 375–400 bars pressure and fluid/rock mass ratios of 0.5–1.0, to assess the role of temperature, basalt/diabase chemistry and texture on heavy metal and sulfur mobility during hydrothermal alteration.Alteration of basalt/diabase is characterized by cation fixation and hydrolysis reactions which show increased reaction progress with increasing temperature at constant pressure. Correspondingly, pH in a series of 400 bar experiments ranges from 4.8 to 2.7 at 350 and 425°C, respectively and is typically lower for alteration of a SiO₂-rich crystalline basalt than for other rock types, due, in part, to relatively high SiO₂ concentrations in solution. High SiO₂ concentrations stabilize hydrous Na- and Ca-rich alteration phases, causing pH to decrease according to reactions such as: 3.0 CaAl₂Si₂O₈ + 1.0 Ca⁺⁺ + 2.0 H₂O = 2.0 Ca₂Al₃Si₃O₁₂(OH) + 2.0 H⁺Phases experimentally produced include: mixed layer chlorite/smectite, Ca-rich amphibole and clinozoisite. Clinozoisite was identified as a replacement product of plagioclase from diabase-solution interaction experiments.In direct response to H⁺ production, dissolved Fe, Mn and H₂S concentrations increase dramatically. For early-stage reaction, H₂S typically exceeds Fe and Mn. However, at 425°C and after long-term reaction at 400°C, H₂S is lost from solution, apparently in response to pyrite replacement of oxide and silicate phases.Pyrrhotite formed at temperatures ≤ 375°C, whereas magnetite was identified in all run products, except from basalt glass alteration.Cu and Zn concentrations in solution are not simple functions of pH. These metals achieve greatest solubility in fluids from experiments at 375–400°C, except when basalt glass is used as a reactant. The relatively low concentrations of these species in solution during basalt glass reaction may be due to adsorption by fine grained alteration phases.     

Adsorption of copper (II) on mesoporous silica: the effect of nano-scale confinement

Nano-scale spatial confinement can alter chemistry at mineral–water interfaces. These nano-scale confinement effects can lead to anomalous fate and transport behavior of aqueous metal species. When a fluid resides in a nanoporous environments (pore size under 100 nm), the observed density, surface tension, and dielectric constant diverge from those measured in the bulk. To evaluate the impact of nano-scale confinement on the adsorption of copper (Cu²⁺), we performed batch adsorption studies using mesoporous silica. Mesoporous silica with the narrow distribution of pore diameters (SBA-15; 8, 6, and 4 nm pore diameters) was chosen since the silanol functional groups are typical to surface environments. Batch adsorption isotherms were fit with adsorption models (Langmuir, Freundlich, and Dubinin–Radushkevich) and adsorption kinetic data were fit to a pseudo-first-order reaction model. We found that with decreasing pore size, the maximum surface area-normalized uptake of Cu²⁺ increased. The pseudo-first-order kinetic model demonstrates that the adsorption is faster as the pore size decreases from 8 to 4 nm. We attribute these effects to the deviations in fundamental water properties as pore diameter decreases. In particular, these effects are most notable in SBA-15 with a 4-nm pore where the changes in water properties may be responsible for the enhanced Cu mobility, and therefore, faster Cu adsorption kinetics.     

Possible implications of modal mineralogy for melting in mantle lherzolites

The melting reaction at the solidus of mantle peridotite is commonly peritectic in nature, with liquid and one or more solid phases produced upon melting. In some situations, one of the phases participating on the reactant side of the reaction is present in low abundance. This article explores the possible effects of the low abundance of a reactant phase on the melting behavior of mantle peridotite.For example, spinel lherzolite begins to melt via the peritectic reaction, clinopyroxene + orthopyroxene + spinel = olivine + liquid in the ∼1- to 2-GPa pressure range. In natural spinel lherzolites, spinel is a modally minor mineral and may be infrequently in contact with both clinopyroxene and orthopyroxene. If these mutual contacts are insufficient to generate an interconnected melt, then significant melting may not occur until a combination of minerals that are modally abundant and in contact begin to melt. This scenario could have implications for the physical process of melting and for the timing of formation of an interconnected melt network and separation of the melt from the residue.To begin to investigate this possibility, the spatial relationships between the constituent minerals in two fertile spinel lherzolites were determined by elemental mapping with the electron microprobe. Olivine, orthopyroxene, and clinopyroxene are of similar size, whereas the spinel was smaller and interstitial. Spinel and clinopyroxene are frequently in contact, but mutual contacts of spinel, clinopyroxene, and orthopyroxene are rare. Because of the changes in modal mineralogy anticipated for these lherzolites with increasing temperature, these mutual contacts will be even less common at the solidus. Therefore, an interconnected, potentially extractable, melt may not occur by the solidus spinel + orthopyroxene + clinopyroxene melting reaction.     

Geochemistry and geochronology of proterozoic tholeiite dykes of east antarctica: evidence for mantle metasomatism

Two episodes of tholeiite dyke emplacement have been identified in Archaean high-grade metamorphics of the Napier Complex in Enderby Land. Middle Proterozoic Amundsen dykes are typical continental tholeiites and most of the chemical variation in individual suites can be explained in terms of different degrees of partial melting and low-pressure crystal fractionation. Group I Amundsen tholeiites were derived from a relatively homogeneous source region 1,190±200 m.y. ago, whereas that of the group II Amundsen tholeiites was chemically and isotopically heterogeneous. Group II dykes have various degrees of enrichment in incompatible elements, and commonly show normalised trace element abundance patterns with negative Nb anomalies. These features imply variable metasomatism of the source region by a volatile-rich fluid phase (rather than a melt of any observed igneous composition) enriched in K, Rb, Ba, Th, and possibly La and Ce.Early Proterozoic (2,350±48 m.y.) tholeiites were emplaced at considerable depths in the crust during the waning stages of granulite-facies metamorphism and include a high-Mg suite of possible komatiitic affinity, ranging in composition from hypersthene-rich tholeiite (norite) to quartz-rich tholeiite. They tend to have higher ratios of highly to moderately incompatible elements (e.g., K/Zr, K/Ce), and larger Nb anomalies (i.e., higher K/Nb) compared with middle Proterozoic tholeiites, suggesting derivation from more enriched source regions. Isotopic data are not compatible with significant crustal contamination, but constrain source metasomatism to a time immediately before emplacement. Metasomatism of the source region of the much younger group I tholeiites may have been contemporaneous with that of the high-Mg suite.     

Oxidation of the Kaapvaal lithospheric mantle driven by metasomatism

The oxidation state, reflected in the oxygen fugacity (fO₂), of the subcratonic lithospheric mantle is laterally and vertically heterogeneous. In the garnet stability field, the Kaapvaal lithospheric mantle becomes progressively more reducing with increasing depth from Δlog fO₂ FMQ-2 at 110 km to FMQ-4 at 210 km. Oxidation accompanying metasomatism has obscured this crystal-chemical controlled depth-fO₂ trend in the mantle beneath Kimberley, South Africa. Chondrite normalized REE patterns for garnets, preserve evidence of a range in metasomatic enrichment from mild metasomatism in harzburgites to extensive metasomatism by LREE-enriched fluids and melts with fairly unfractionated LREE/HREE ratios in phlogopite-bearing lherzolites. The metasomatized xenoliths record redox conditions extending up to Δlog fO₂ = FMQ, sufficiently oxidized that magnesite would be the stable host of carbon in the most metasomatized samples. The most oxidized lherzolites, those in or near the carbonate stability field, have the greatest modal abundance of phlogopite and clinopyroxene. Clinopyroxene is modally less abundant or absent in the most reduced peridotite samples. The infiltration of metasomatic fluids/melts into diamondiferous lithospheric mantle beneath the Kaapvaal craton converted reduced, anhydrous harzburgite into variably oxidized phlogopite-bearing lherzolite. Locally, portions of the lithospheric mantle were metasomatized and oxidized to an extent that conversion of diamond into carbonate should have occurred. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

The origin of faceted garnets in sandstones: dissolution or overgrowth?

Faceted garnets from a wide range of geological ages, environments and locations have been studied in polished grain mounts by a combination of backscattered electron microscopy and elemental mapping using energy-dispersive X-ray analysis. In all cases, the areas apparently showing positive relief on the faceted garnet surfaces are compositionally identical to the adjacent grain cores despite a wide variation in detrital garnet compositions. In one case, zoning within the grain core can be traced into the faceted areas on the grain surface. Thus, faceted areas must be considered to form part of the original detrital grains. Together with previously published studies on experimental garnet etching, thermodynamic conditions for garnet growth, textural relationships between faceted garnets and authigenic and detrital phases, and distribution of faceted garnets in the subsurface, this paper provides conclusive proof that faceted garnet surfaces form as a result of dissolution, not overgrowth.