Titanium- and water-rich metamorphic olivine in high-pressure serpentinites from the Voltri Massif (Ligurian Alps,Italy): evidence for deep subduction of high-field strength and fluid-mobile elements

Titanium- and water-rich metamorphic olivine (Fo 86–88) is reported from partially dehydrated serpentinites from the Voltri complex, Ligurian Alps. The rocks are composed of mostly antigorite and olivine in addition to magnetite, chlorite, clinopyroxene and Ti-clinohumite. In situ secondary ion mass spectrometry (SIMS) data show that metamorphic olivine has very high and strongly correlated H₂O (up to 0.7 wt%) and TiO₂ contents (up to 0.85 wt%). Ti-rich olivine shows colourless to yellow pleochroism. Olivine associated with Ti-clinohumite contains low Ti, suggesting that Ti-rich olivine is not the breakdown product of Ti-clinohumite. Fourier transform infrared spectroscopy (FTIR) absorption spectra show peaks of serpentine, Ti-clinohumite and OH-related Si vacancies. Combining FTIR and SIMS data, we suggest the presence of clustered planar defects or nanoscale exsolutions of Ti-clinohumite in olivine. These defects or exsolutions contain more H₂O (x ~ 0.1 in the formula 4Mg₂SiO₄·(1?x)Mg(OH,F)₂·xTiO₂) than Ti-clinohumite in the sample matrix (x = 0.34–0.46). In addition to TiO₂ and H₂O, secondary olivine contains significant Li (2–60 ppm), B (10–20 ppm), F (10–130 ppm) and Zr (0.9–2.1 ppm). It is enriched in ¹¹B (δ¹¹B = +17 to +23 ‰). Our data indicate that secondary olivine may play a significant role in transporting water, high-field strength and fluid-mobile elements into the deeper mantle as well as introduce significant B isotope anomalies. Release of hydrogen from H₂O-rich olivine subducted into the deep mantle may result in strongly reduced mantle domains.     

Near-surface soil stabilization by enzyme-induced carbonate precipitation for fugitive dust suppression

Acta Geotechnica - To resolve the environmental and sustainability issues from fugitive dust emission and conventional mitigation methods, multiple experiments were conducted to evaluate the...     

Distinct sedimentary processes reflected in the isotopic signatures of dolomitic concretions in the Miocene Pohang Basin (southwestern East Sea)

Dolomitic concretions in diatomaceous hemipelagic sediments of the Miocene Pohang Basin in the southwestern East Sea (Sea of Japan) preserve distinct signals of two independent sedimentary processes, which controlled the extents of isotopic compositions. Variable δ¹⁸O (−9.1‰ to +0.7‰) and high δ¹³C (+3.1‰ to +17.9‰) values suggest that the concretions formed in the methanogenic zone with alteration of the residual mid-Miocene seawater by volcanogenic sediments. Remarkable δ¹⁸O and δ¹³C values show a strong linear relationship, indicating that distinctly independent depositional processes operated during the formation of the concretions. The degree of methanogenesis was enhanced during rapid hemipelagic sedimentation of organic-rich particles, resulting in higher δ¹³C values, and the effect of volcaniclastics was diluted, maintaining the original properties of ambient mid-Miocene seawater. In contrast, lower δ¹⁸O and ⁸⁷Sr/⁸⁶Sr values characterize the effect of volcaniclastic sediments that were transported by intermittent gravity flows and interacted with mid-Miocene seawater. The input of volcaniclastic sediment probably degraded the role of methanogenesis by lowering the contents of organic matter and thereby decreased the δ¹³C values within the concretions. Isotopic signals recorded within the concretions highlight understanding of the depositional environment and evolution of the pore-water chemistry.     

Geology and Hydrothermal Alteration of the Milyang Pyrophyllite Deposit, Southeast Korea

Abstract: The Milyang pyrophyllite deposit, which is embedded in the Late Cretaceous Yuchon Group of the Kyongsang Supergroup, is one of the largest hydrothermal clay deposits in the Kyongsang basin, southeast Korea. Host rocks of the deposit are porphyritic andesite lava and minor andesitic lapilli tuff. In the Milyang district, a hydrothermally altered zone is about 2 × 3 km in extent; we can recognize the concentric arrangement of advanced argillic, propylitic, and sericitic alteration zones from the central to peripheral parts of the zone. The Milyang pyrophyllite deposit forms a part of the advanced argillic alteration zone. The Milyang pyrophyllite deposit is subdivided into the following four zones based on mineral assemblages: the pyrophyllite zones 1, 2, 3, and the silicified zone. The pyrophyllite zone 1, which occupies the central part of the deposit, comprises mainly pyrophyllite, kaolinite, and diaspore without quartz. Diaspore nodules often concentrate in beds 40–50 cm thick. Andalusite, dumortierite, and tourmaline locally occur as network veins, crack‐filler, or small spherulitic spots. The Al₂O₃ content of the ore ranges from 27 to 36 wt%. The pyrophyllite zone 2, which constitutes a major part of the deposit, comprises mainly pyrophyllite, kaolinite, and quartz. The Al₂O₃ content of the ore ranges from 15 to 24 wt%. The pyro‐phyllite zone 3 is the hematite‐rich marginal facies of the deposit. The silicified zone, which occurs as beds and septa, is mostly composed of quartz with minor pyrophyllite and kaolinite; the SiO₂ contents range from 79 to 90 wt%. Comparing chemical compositions of the high‐Al ores with those of unaltered host andesite, the Fe, Ca, alkalis, HFSE, and HREE contents are significantly depleted, whereas S, B, As, Sr, and LREE are enriched. The hydrothermal alteration of the Milyang pyrophyllite deposit can be classified into the following four stages: 1) extensive sericitic and propylitic alteration, 2) medium‐temperature (200–250°C) advanced argillic alteration, 3) high‐temperature (250–350°C or more) advanced argillic alteration, and 4) retrograde low‐temperature alteration. The heat and some volatile components such as B and S would be derived from the Pulguksa Granite intruded underneath the deposit.     

Endolithic biodegradation of cool-water skeletal carbonates on Scott shelf, northwestern Vancouver Island, Canada

Biodegradation of shell material is widespread in the cool-water skeletal carbonate deposits on Scott shelf, northwestern Vancouver Island, and is especially evident in the large aragonitic bivalves, Glycymeris and Humilaria, major primary sediment contributors. Ten types of endolithic microborings have been identified in the shells, including representatives of green algae (e.g., Ostreobium quekettii), blue-green algae (e.g., Plectonema terebrans, ?Scytonema sp.), fungi, bacteria and clionid sponges, as well as macroborings of phoronids, polychaetes and naticid gatropods. Microcrystalline carbonate is not precipitated in vacated bores. Boring physically weakens the shells, rendering them more prone to mechanical abrasion during sediment transport and bioturbation, and to biological abrasion by grazing benthos. Tumbling experiments demonstrate that the rate of carbonate mud production is much greater for bored as compared to fresh bivalve shells, and that mud production rates decrease with tumbling time because most endolithic microborings are confined to the periphery of grains. Boring also increases significantly the porosity and surface area of skeletal grains, and destroys their organic matrix, making them susceptible to maceration and dissolution on cool-water shelves. Fostered by the generally low rates of carbonate production and accumulation, many aragonitic bivalve shells on Scott shelf have become thoroughly degraded through a combination of endolithic microboring, maceration and dissolution within about 1000 years in ambient sea water. In geologic terms, such selective taphonomic loss of skeletal material may be considerable in ancient temperate-shelf limestones and should be evaluated when interpreting their paleoecology and paleoenvironments.     

Zinc-rich Pyrite from the TAG Active Mound, the TAG Hydrotherma Field, Mid-Atlantic Ridge

Abstract: Pyrite rich in Zn, up to 3.1 wt%, was found in the TAG active mound of the TAG hydrothermal field, the slow-spreading Mid-Atlantic Ridge at 26°08'N and 44°49'W. The Zn-rich pyrite is characterized by an optical homogeneity, a homogeneous distribution of Zn in the back-scattered electron images, both at a magnification of about 500, a negative correlation between Fe and Zn contents of the pyrite and a rather small unit cell edge (a₀ = 5.4117 ± 0.0008Å), strongly indicating that the detected Zn is present in the pyrite in solid solution. Such Zn concentrations are observed exclusively in dendritic pyrite, suggesting that the Znrich pyrite grew from hydrothermal fluids of a high degree of supersaturation due to quenching on the seafloor.     

Lower crustal melting and the role of open-system processes in the genesis of syn-orogenic quartz diorite–granite–leucogranite associations: constraints from Sr–Nd–O isotopes from the Bandombaai Complex, Namibia

The Bandombaai Complex (southern Kaoko Belt, Namibia) consists of three main intrusive rock types including metaluminous hornblende- and sphene-bearing quartz diorites, allanite-bearing granodiorites and granites, and peraluminous garnet- and muscovite-bearing leucogranites. Intrusion of the quartz diorites is constrained by a U–Pb zircon age of 540±3 Ma.

Quartz diorites, granodiorites and granites display heterogeneous initial Nd- and O isotope compositions (_{Nd (540 Ma)}=−6.3 to −19.8; δ¹⁸O=9.0–11.6‰) but rather low and uniform initial Sr isotope compositions (⁸⁷Sr/⁸⁶Sr_initial=0.70794–0.70982). Two leucogranites and one aplite have higher initial ⁸⁷Sr/⁸⁶Sr ratios (0.70828–0.71559), but similar initial _Nd (−11.9 to −15.8) and oxygen isotope values (10.5–12.9‰). The geochemical and isotopic characteristics of the Bandombaai Complex are distinct from other granitoids of the Kaoko Belt and the Central Zone of the Damara orogen. Our study suggests that the quartz diorites of the Bandombaai Complex are generated by melting of heterogeneous mafic lower crust. Based on a comparison with results from amphibolite-dehydration melting experiments, a lower crustal garnet- and amphibole-bearing metabasalt, probably enriched in K₂O, is a likely source rock for the quartz diorites. The granodiorites/granites show low Rb/Sr (<0.6) ratios and are probably generated by partial melting of meta-igneous (intermediate) lower crustal sources by amphibole-dehydration melting. Most of the leucogranites display higher Rb/Sr ratios (>1) and are most likely generated by biotite-dehydration melting of heterogeneous felsic lower crust. All segments of the lower crust underwent partial melting during the Pan-African orogeny at a time (540 Ma) when the middle crust of the central Damara orogen also underwent high T, medium P regional metamorphism and melting. Geochemical and isotope data from the Bandombaai Complex suggest that the Pan-African orogeny in this part of the orogen was not a major crust-forming episode. Instead, even the most primitive rock types of the region, the quartz diorites, represent recycled lower crustal material.     

Rare earth elements in Huronian (Lower Proterozoic) sedimentary rocks: Composition and evolution of the post-Kenoran upper crust

The Huronian sequence (Lower Proterozoicl. north of Lake Huron, contains tillites and abundant fine-grained sedimentary rocks. Analyses of rare earth elements (REE) in the matrix of tillite samples from the Gowganda Formation (~ 2.3 Gal is considered to be a reasonable estimate of upper crustal REE abundances for the region north of Lake Huron at the time of Gowganda deposition. The average is characterized by a moderately steep pattern (σLREEσHREE = 9.1) and a slight negative europium anomaly ($\text{Eu}\text{Eu1}\text{= 0.89}$). This pattern is similar to estimates of the composition of the surface of the Canadian Shield and is intermediate between estimates of typical Archean and post-Archean sedimentary rocks. REE patterns for framework granitoid clasts from the tillite suggest that K-rich granites, which were apparently unimportant in the formation of Archean sedimentary rocks, were abundant in the source regions of the Gowganda Formation. This may explain the intermediate nature of the Gowganda pattern.Comparison of the tillites and associated Gowganda mudstones suggests that previous estimates of upper crustal REE abundances, which were based on the analyses of fine-grained sedimentary rocks, may be systematically high. Relative distributions, however, are the same.Analyses of mudstones from the McKim. Pecors. Serpent Gowganda Lorrain and Gordon Lake Formations suggest rapid evolution in the composition of the exposed upper crust at the close of the Kenoran orogeny. REE patterns at the base of the Huronian are similar to typical Archean sedimentary rocks. REE characteristics change up section: patterns at the top resemble typical post-Archean sedimentary rocks.It is inferred that an essentially episodic change from an early exposed upper crust dominated by a tonalite-greenstone suite to one approximating granodioritic composition is recorded in Huronian sedimentary rocks. A deviation from the evolutionary trend of the Huronian, documented in the Gowganda Formation, may be related to the glacial origin of the Gowganda.     

The behaviour of dissolved organic material,iron and manganese in estuarine mixing

Fractionation by ultra-filtration of the dissolved organic material (DOM) in the River Beaulieu, with typical concentrations of dissolved organic carbon (DOC) of 7–8 mg C/l, showed it to be mainly in the nominal molecular weight range of 10³–10⁵, with 16–23% of the total DOC in the fraction > 10⁵. The molecular weight distribution of DOM in the more alkaline River Test (average DOC, 2 mg C/l) was similar. In the River Beaulieu water, containing 136–314 βg Fe/l in ‘dissolved’ forms, 90% or more of this Fe was in the nominal molecular weight fraction > 10⁵. Experiments showed that DOM of nominal molecular weight <10⁵ could stabilize Fe(III) in ‘dissolved’ forms. The concentrations of ‘dissolved’ Fe in the river water probably reflect the presence of colloidal Fe stabilized by organic material and this process may influence the apparent molecular weight of the DOM. Dissolved. Mn (100–136 βg/l) in the River Beaulieu was mainly in true solution, probably as Mn(II), with some 30% in forms of molecular weight greater than ca 10⁴.During mi xing in the Beaulieu Estuary, DOC and dissolved Mn behave essentially conservatively. This contrasts with the removal of a large fraction of the dissolved Fe (Holliday and LISS, 1976, Est. Coastal Mar. Sci. 4, 349–353). Concentrations of lattice-held Fe and Mn in suspended particulate material were essentially uniform in the estuary, at 3.2 and 0.012%, respectively, whereas the non-lattice held fractions decreased markedly with increase in salinity. For Mn the decrease was linear and could be most simply accounted for by the physical mixing of riverborne and marine participates, although the possibility that some desorption occurs is not excluded. The non-linear decrease in the concentration of non-lattice held Fe in particulates reflected the more complex situation in which physical mixing is accompanied by removal of material from the ‘dissolved’ fraction.     

Model-based remote sensing algorithms for particulate organic carbon (POC) in the Northeastern Gulf of Mexico

Hydrographic data, including particulate organic carbon (POC) from the Northeastern Gulf of Mexico (NEGOM) study, were combined with remotely-sensed SeaWiFS data to estimate POC concentration using principal component analysis (PCA). The spectral radiance was extracted at each NEGOM station, digitized, and averaged. The mean value and spurious trends were removed from each spectrum. De-trended data included six wavelengths at 58 stations. The correlation between the weighting factors of the first six eigenvectors and POC concentration were applied using multiple linear regression. PCA algorithms based on the first three, four, and five modes accounted for 90, 95, and 98% of total variance and yielded significant correlations with POC with R ² = 0.89, 0.92, and 0.93. These full waveband approaches provided robust estimates of POC in various water types. Three different analyses (root mean square error, mean ratio and standard deviation) showed similar error estimates, and suggest that spectral variations in the modes defined by just the first four characteristic vectors are closely correlated with POC concentration, resulting in only negligible loss of spectral information from additional modes. The use of POC algorithms greatly increases the spatial and temporal resolution for interpreting POC cycling and can be extrapolated throughout and perhaps beyond the area of shipboard sampling.