The role of volatile exsolution and sub-solidus fluid/rock interactions in producing high Fe/Fe ratios in siliceous igneous rocks

Highly differentiated igneous rocks can, in some cases, have ⁵⁶Fe/⁵⁴Fe ratios that are significantly higher than those of mafic- to intermediate-composition igneous rocks. Iron isotope compositions were obtained for bulk rock, magnetite, and Fe silicates from well-characterized suites of granitic and volcanic rocks that span a wide range in major- and trace-element contents. Sample suites studied include granitoids from Questa, N.M. (Latir volcanic field) and the Tuolumne Intrusive Series (Sierra Nevada batholith), and volcanic rocks from Coso, Katmai, Bishop Tuff, Grizzly Peak Tuff, Seguam Island, and Puyehue volcano. The rocks range from granodiorite to high-silica granite and basalt to high-silica rhyolite. The highest δ⁵⁶Fe values (up to +0.31‰) are generally restricted to rocks that have high Rb (>100 ppm), Th (>∼15 ppm) and SiO₂ (>70 wt.%) but low Fe (<2 wt.% total Fe as Fe₂O₃) contents. Magnetite separated from these rocks has high δ⁵⁶Fe values, whereas Fe silicates have δ⁵⁶Fe values close to zero. Although in principle crystal fractionation might explain the high δ⁵⁶Fe values, trace-element ratios in high-δ⁵⁶Fe igneous rocks indicate that crystal fractionation is an unlikely explanation. The highest δ⁵⁶Fe values occur in volcanic and plutonic rocks that contain independent evidence for fluid exsolution, including sub-chondritic Zr/Hf ratios, suggesting that loss of a low-δ⁵⁶Fe ferrous chloride fluid is the most likely explanation for the high δ⁵⁶Fe values in the bulk rocks. Based on magnetite solubility in chloride solutions and predicted Fe isotope fractionations among Fe silicates, magnetite, and ferrous chloride fluids, the increase in δ⁵⁶Fe values of bulk rocks may be explained by isotopic exchange between magnetite and , which predicts an increase in the δ⁵⁶Fe values of magnetite upon fluid exsolution. This model is consistent with the δ⁵⁶Fe values measured in this study for bulk rocks, as well as magnetite and Fe silicates. Our results suggest that fluid exsolution from siliceous hydrous magmas, which sometimes produce porphyry-style Cu, Mo, or Cu-Au mineralization, may be traced using Fe isotopes.     

Impact of human activities on the central Mediterranean offshore: Evidence from Hg distribution in box-core sediments from the Ionian Sea

Total Hg concentrations have been measured for five box-core sediments collected seawards of the Augusta industrial area (SE Sicily). In more coastal sediments, upcore increasing Hg concentrations, exceeding the Hg background concentration estimated for the Strait of Sicily, indicate Hg contamination over time due to the industrial area development. Strong correlation between total organic C (TOC) and Hg concentrations was found only for core BX2, that displays organic C to total N (C/N) ratios indicative of autochthonous organic matter. For other sediments, high Hg enrichment factors with respect to TOC indicate, in addition to Hg trapping by TOC, other factors as responsible for Hg accumulation. In the presence of some contribution of detrital organic matter, Hg is mainly adsorbed onto the mineral component of the bottom sediments probably because TOC is saturated by Hg excess. Contaminant impact affected also the open sea environment. Main drivers of Hg flux towards the offshore were dredged materials, which repeatedly discharged sediment, resulting in substantial increases in TOC contents and high C/N ratios. Consistent with the geochemistry of recent turbidites, these anomalous sedimentary inputs induced sediment redox environment modifications, constrained by Mn peaks, which affected Hg distribution.     

Multiscale Variability of Twenty-Two Coastal Phytoplankton Time Series: a Global Scale Comparison

We provide an introduction and a foreword to the Special Issue “Phytoplankton Time Series in Estuaries and Coastal Ecosystems”. This issue includes long-term investigations (10–40 years) of 22 coastal ecosystems and a comparative analysis of chlorophyll a from 84 time series. The results and conclusions provided by these studies help to illuminate the disparities and similarities in long-term phytoplankton dynamics among a wide range of coastal systems and provide insight into the major driving factors responsible for short- and long-term trends in phytoplankton communities.     

Coupling the terrestrial hydrology model with biogeochemistry to the integrated LAND surface model: Amazon Basin applications

ABSTRACT

We coupled the hydrologic routing and flood dynamics model Terrestrial Hydrology Model with Biogeochemistry (THMB) to the Integrated LAND Surface Model (INLAND) and compared simulations of the discharge and flood extent area against gauge station and satellite-based information in the Amazon Basin. The coupled model represents well the seasonality of the flooding and discharge, but underestimates both of them. This can be related to an already discussed underestimate of the precipitation in the east of the Andes Mountains. A photosynthesis limitation on the flooded area was also included, showing changes in plant productivity and reduction in vegetation carbon stocks. Despite its limitations, the model proves to be a valuable tool for studies of the hydrological cycle and flood dynamics response to climate change projections, allowing it to be used to represent the feedbacks between continental surface water cycle and vegetation.     

The composition of garnet in garnet-rich rocks in the southern Proterozoic Curnamona Province, Australia: an indicator of the premetamorphic physicochemical conditions of formation

Garnet-rich rocks occur throughout the Proterozoic southern Curnamona Province, Australia, where they are, in places, spatially related to Broken Hill-type Pb-Zn-Ag deposits. Fine-scale bedding in these rocks, their conformable relationship with enclosing metasedimentary rocks, and their enrichment in Mn and Fe suggest that they are metamorphosed chemical precipitates. They formed on the floor of a 1.69?Ga continental rift basin from hydrothermal fluids mixed with seawater and detritus. Garnet in garnet-quartz and garnet-amphibole rocks is generally light rare earth element (LREE) depleted, and has flat heavy REE (HREE) enriched chondrite-normalized REE patterns, and negative Eu anomalies (Eu/Eu*?<?1). Garnet in garnet-rich rocks from the giant Broken Hill deposit has similar REE patterns and either positive (Eu/Eu*?>?1) or negative Eu anomalies. Manganese- and Mn-Ca-rich, Fe-poor garnets in garnetite, garnet-hedenbergite, and garnet-cummingtonite rocks at Broken Hill have Eu/Eu*?>?1, whereas garnet in Mn-poor, Fe-rich quartz garnetite and quartz-garnet-gahnite rocks from Broken Hill, and quartz garnetite from other locations have Eu/Eu*?<?1. The REE patterns of garnet and its host rock and interelement correlations among REEs and major element contents in garnet and its host rock indicate that the Eu anomaly in garnet reflects that of its host rock and is related to the major element composition of garnet and its host rock. The value of Eu/Eu* in garnet is related to its Mn, Fe, and Ca content and that of its host rock, and the distribution of REEs among garnet and accessory phases (e.g., feldspar). Positive Eu anomalies reflect high amounts of Eu that was preferentially incorporated into Mn- and Mn-Ca-rich oxides and carbonates in the protolith. In contrast, Eu/Eu*?<?1 indicates the preferential discrimination against Eu by Fe-rich, Mn-poor precursor minerals. Precursors to Mn-rich garnets at Broken Hill formed by precipitation from cooler and more oxidized hydrothermal fluids compared to those that formed precursors to Mn-poor, Fe-rich garnet at Broken Hill and the other locations. Garnet from the Broken Hill deposit is enriched in Zn (> 400?ppm), Cr (> 140?ppm), and Eu (up to 6?ppm and positive Eu anomalies), and depleted in Co, Ti, and Y compared to garnet in garnet-rich rocks from other localities. These values, as well as MnO contents ?>?15 wt. % and Eu/Eu*?>?1 are only found at the Broken Hill deposit and are good indicators of the presence of Broken Hill-type mineralization.     

Comparison of the quantitative determination of soil organic carbon in coastal wetlands containing reduced forms of Fe and S

The performance of the Walkley–Black wet oxidation chemical method for soil organic carbon (SOC) determination in coastal wetland soils (mangroves, coastal lagoons, and hypersaline tidal flats) was evaluated in the state of Ceará along the semiarid coast of Brazil, assessing pyrite oxidation and its effects on soil C stock (SCS) quantification. SOC determined by the chemical oxidation method (C_WB) was compared to that assessed by means of a standard elemental analyzer (C_EA) for surficial samples (<30 cm depth) from the three wetland settings. The pyrite fraction was quantified in various steps of the chemical oxidation method, evaluating the effects of pyrite oxidation. Regardless of the method used, and consistent with site-specific physicochemical conditions, higher pyrite and SOC contents were recorded in the mangroves, whereas lower values were found in the other settings. C_WB values were higher than C_EA values. Significant differences in SCS calculations based on C_WB and C_EA were recorded for the coastal lagoons and hypersaline tidal flats. Nevertheless, the C_WB and C_EA values were strongly correlated, indicating that the wet oxidation chemical method can be used in such settings. In contrast, the absence of correlation for the mangroves provides evidence of the inadequacy of this method for these soils. Air drying and oxidation decrease the pyrite content, with larger effects rooted in oxidation. Thus, the wet oxidation chemical method is not recommended for mangrove soils, but seems appropriate for SOC/SCS quantification in hypersaline tidal flat and coastal lagoon soils characterized by lower pyrite contents.     

Evidence that Synchrotron Emission from Nonthermal Electrons Produces the Increasing Submillimeter Spectral Component in Solar Flares

We investigate the origin of the increasing spectra observed at submillimeter wavelengths detected in the flare on 2 November 2003 starting at 17:17 UT. This flare, classified as an X8.3 and 2B event, was simultaneously detected by RHESSI and the Solar Submillimeter Telescope (SST) at 212 and 405 GHz. Comparison of the time profiles at various wavelengths shows that the submillimeter emission resembles that of the high-energy X rays observed by RHESSI whereas the microwaves observed by the Owens Valley Solar Array (OVSA) resemble that of ∼50 keV X rays. Moreover, the centroid position of the submillimeter radiation is seen to originate within the same flaring loops of the ultraviolet and X-ray sources. Nevertheless, the submillimeter spectra are distinct from the usual microwave spectra, appearing to be a distinct spectral component with peak frequency in the THz range. Three possibilities to explain this increasing radio spectra are discussed: (1) gyrosynchrotron radiation from accelerated electrons, (2) bremsstrahlung from thermal electrons, and (3) gyrosynchrotron emission from the positrons produced by pion or radioactive decay after nuclear interactions. The latter possibility is ruled out on the grounds that to explain the submillimeter observations requires 3000 to 2×10⁵ more positrons than what is inferred from X-ray and γ-ray observations. It is possible to model the emission as thermal; however, such sources would produce too much flux in the ultraviolet and soft X-ray wavelengths. Nevertheless we are able to explain both spectral components at microwave and submillimeter wavelengths by gyrosynchrotron emission from the same population of accelerated electrons that emit hard X rays and γ rays. We find that the same 5×10³⁵ electrons inferred from RHESSI observations are responsible for the compact submillimeter source (0.5 arcsec in radius) in a region of 4500 G low in the atmosphere, and for the traditional microwave spectral component by a more extended source (50 arcsec) in a 480 G magnetic field located higher up in the loops. The extreme values in magnetic field and source size required to account for the submillimeter emission can be relaxed if anisotropy and transport of the electrons are taken into account.     

Holocene small mammals hunted by owls and humans in southern Brazil: taphonomic evidence and biological significance

Understanding resource utilization and economic diversification amongst Holocene hunter‐gatherers in southern Brazil requires in‐depth taphonomic analysis of faunal assemblages. Three Early to Late Holocene archaeological sites (Garivaldino, Pilger and Sangão) in Rio Grande do Sul State, southern Brazil, revealed large assemblages of small mammal (?1 kg) remains, composed mainly of rodents. To appreciate depositional processes of fauna in relation to human consumption, taphonomic attributes and processes were evaluated. The results indicated that the remains accumulated through different antemortem taphonomic pathways, apparently linked to the size and natural history of the species represented. The small‐ and medium‐sized (<150 g) cricetid rodents (e.g. Pseudoryzomys simplex and Sooretamys angouya) were represented by a low proportion of teeth with lightly digestive corrosion suggesting that they were derived from the predatory activity of owls, possibly Tyto alba. In contrast, large‐sized cricetids (>150 g; Kunsia tomentosus, Gyldenstolpia sp. and Holochilus sp.), and several caviomorph rodents with aggregated spatial distributions (Echimyidae (?Dicolpomys fossor, Phyllomys sp., ?Clyomys riograndensis and ?Euryzygomatomys mordax), Caviidae (Cavia sp.) and Ctenomyidae (Ctenomys sp.)) showed evidence of thermoalteration patterns and cut marks on bones, suggesting human exploitation. A postmortem depositional environment was deduced from dendritic and branched patterns of rootlet etching, apparent mostly at Garivaldino and Pilger. Polished areas and holes on bone surfaces, and impregnation of manganese showed moderate (Sangão) or low (Garivaldino and Pilger) incidence, pointing to water transport under moderate (Pilger) and low (Garivaldino and Sangão) energy over short distances. The results obtained here provide the first clear evidence of early human exploitation of small mammals in southern Brazil, suggesting a diversification of economies. In addition, as several of the recorded rodents are today regionally or biologically extinct, a preliminary discussion about the potential impact of humans on this process is provided.