The effect of dissolved barium on biogeochemical processes at cold seeps

A numerical model was applied to investigate and quantify the biogeochemical processes fueled by the expulsion of barium and methane-rich fluids in the sediments of a giant cold-seep area in the Derugin Basin (Sea of Okhotsk). Geochemical profiles of dissolved Ba²⁺, Sr²⁺, Ca²⁺, SO₄²⁻, HS⁻, DIC, I⁻ and of calcium carbonate (CaCO₃) were fitted numerically to constrain the transport processes and the kinetics of biogeochemical reactions. The model results indicate that the anaerobic oxidation of methane (AOM) is the major process proceeding at a depth-integrated rate of 4.9 μmol cm⁻² a⁻¹, followed by calcium carbonate and strontian barite precipitation/dissolution processes having a total depth-integrated rate of 2.1 μmol cm⁻² a⁻¹. At the low seepage rate prevailing at our study site (0.14 cm a⁻¹) all of the rising barium is consumed by precipitation of barite in the sedimentary column and no benthic barium flux is produced. Numerical experiments were run to investigate the response of this diagenetic environment to variations of hydrological and biogeochemical conditions. Our results show that relatively low rates of fluid flow (<∼5 cm a⁻¹) promote the dispersed precipitation of up to 26 wt% of barite and calcium carbonate throughout the uppermost few meters of the sedimentary column. Distinct and persistent events (several hundreds of years long) of more vigorous fluid flow (from 20-110 cm a⁻¹), instead, result in the formation of barite-carbonate crusts near the sediment surface. Competition between barium and methane for sulfate controls the mineralogy of these sediment precipitates such that at low dissolved methane/barium ratios (<4-11) barite precipitation dominates, while at higher methane/barium ratios sulfate availability is limited by AOM and calcium carbonate prevails. When seepage rates exceed 110 cm a⁻¹, barite precipitation occurs at the seafloor and is so rapid that barite chimneys form in the water column. In the Derugin Basin, spectacular barite constructions up to 20 m high, which cover an area of roughly 22 km² and contain in excess of 5 million tons of barite, are built through this process. In these conditions, our model calculates a flux of barium to the water column of at least 20 μmol cm⁻² a⁻¹. We estimate that a minimum of 0.44 × 10⁶ mol a⁻¹ are added to the bottom waters of the Derugin Basin by cold seep processes, likely affecting the barium cycle in the Sea of Okhotsk.     

Organochlorine residues,eggshell thickness,and nest success in barn owls from the Chesapeake Bay

Eggs of barn owls (Tyto alba) were collected from 18 nests in offshore duck blinds on the Maryland side of the lower Potomac River estuary in 1972 and 1973 and analyzed for organochlorine residues. DDE was found in 100% of the clutches, PCBs in 89%, and dieldrin in 78%. Eggshell thickness was inversely correlated with concentrations of DDE, DDD, and dieldrin residues. Six of the 18 clutches had mean DDE residues above 5 ppm, and eggshell thickness in these six clutches was significantly less (P<0.001) than in the other 12 clutches. The owls produced 1.7 young per active nest in 1973. This rate is slightly below the reproductive rate needed to maintain a stable population. An estimated 15% of the population carried concentrations of organochlorine residues that may have been detrimental to their reproduction. Passerine birds, taken extensively as food by a small proportion of the population, are believed to have been the source of elevated concentrations of organochlorines in these barn owls.     

Heavy metal content in the stream sediments adjacent to a sanitary landfill

Samples of stream sediments were collected along two streams adjacent to a sanitary landfill. One of the streams drained the landfill directly. In addition, control of background samples were also analyzed from a stream not affected by the landfill. All samples were analyzed for Ag, Zn, Cu, Cd, and Pb content using atomic adsorption techniques. The pH of the three streams were monitored since pH differences in the streams may affect the quantities of metals adsorbed or precipitated on the sediments. The comparison between the content of Ag, Zn, and Cu in the sediments of the two study streams and the same metals in the control sediments indicated the landfill emitted these metals into the two adjacent streams. However, since the Cd and Pb contents in the sediments of both streams were similar to that of the control stream sediments, these metals may not be emitted into the two study streams from the landfill and they represent only background quantities. The comparisons of each metal in the sediments of each stream were made by the use of a metal trend chart, the individual calculated mean metal content values, and by the statistical two sample t-test. No decreasing trends of the quantities of Ag, Zn, or Cu as a function of increasing distance from the landfill was present in the sediments along the stream that drained the landfill directly. These sediments might have been affected by stream action and became mixed with other sediments downstream.     

Fluid entrapment and reequilibration during subduction and exhumation: A case study from the high-grade Nestos shear zone, Central Rhodope, Greece

A fluid inclusion study on metamorphic minerals of successive growth stages was performed on highly deformed paragneisses from the Nestos Shear Zone at Xanthi (Central Rhodope), in which microdiamonds provide unequivocal evidence for ultrahigh-pressure (UHP) metamorphism. The correlation of fluid inclusion density isochores and fluid inclusion reequilibration textures with geothermobarometric data and the relative chronology of micro- and macro-scale deformation stages allow a better understanding of both the fluid and metamorphic evolution along the P–T–d path. Textural evidence for subduction towards the NE is recorded by the orientation of intragranular NE-oriented fluid inclusion planes and the presence of single, annular fluid inclusion decrepitation textures. These textures occur within quartz “foam” structures enclosed in an earlier generation of garnets with prolate geometries and rarely within recrystallized matrix quartz, and reequilibrated both in composition and density during later stages of exhumation. No fluid inclusions pertaining to the postulated ultrahigh-pressure stage for microdiamond-bearing garnet–kyanite–gneisses have yet been found. The prolate shape of garnets developed during the earliest stages of exhumation that is recorded structurally by (L  S) tectonites, which subsequently accommodated progressive ductile SW shearing and folding up to shallow crustal levels. The majority of matrix kyanite and a later generation of garnet were formed during SW-directed shear under plane-strain conditions. Fluid inclusions entrapped in quartz during this stage of deformation underwent density loss and transformed to almost pure CO₂ inclusions by preferential loss of H₂O. Those inclusions armoured within garnet retained their primary 3-phase H₂O–CO₂ compositions. Reequilibration of fluid inclusions in quartz aggregates is most likely the result of recrystallization along with stress-induced, preferential H₂O leakage along dislocations and planar lattice defects which results in the predominance of CO₂ inclusions with supercritical densities. Carbonic fluid inclusions from adjacent kyanite–corundum-bearing pegmatoids and, the presence of shear-plane-parallel fluid inclusion planes within late quartz boudin structures consisting of pure CO₂-fluid inclusions with negative crystal shapes, bear witness of the latest stage of deformation by NE-directed extensional shear.This study shows that the textures of early fluid inclusions that formed already during the prograde metamorphic path can be preserved and used to derive information about the kinematics of subduction that is difficult to obtain from other sources. The textures of early inclusions, together with later generations of unaltered primary and secondary inclusions in metamorphic index minerals that can be linked to specific deformation stages and even P–T conditions, are a welcome supplement for the reconstruction of a rather detailed P–T–d path.     

The end of the Ediacara biota: Extinction,biotic replacement,or Cheshire Cat?

The Ediacaran–Cambrian transition signals a drastic change in both diversity and ecosystem construction. The Ediacara biota (consisting of various metazoan stem lineages in addition to extinct eukaryotic clades) disappears, and is replaced by more familiar Cambrian and Paleozoic metazoan groups. Although metazoans are present in the Ediacaran, their ecological contribution is dwarfed by Ediacaran-type clades of uncertain phylogenetic affinities, while Ediacaran-type morphologies are virtually non-existent in younger assemblages. Three alternative hypotheses have been advanced to explain this dramatic change at, or near, the Ediacaran–Cambrian boundary: 1) mass extinction of most Ediacaran forms; 2) biotic replacement, with early Cambrian organisms eliminating Ediacaran forms; and 3) a Cheshire Cat model, with Ediacaran forms gradually disappearing from the fossil record (but not necessarily going extinct) as a result of the elimination of unique preservational settings, primarily microbial matgrounds, that dominated the Ediacaran. To evaluate these proposed explanations for the biotic changes observed at the Ediacaran–Cambrian transition, environmental drivers leading to global mass extinction are compared to biological factors such as predation and ecosystem engineering. We explore temporal and biogeographic distributions of Ediacaran taxa combined with evaluations of functional guild ranges throughout the Ediacaran. The paucity of temporally-resolved localities with diverse Ediacaran assemblages, combined with difficulties associated with differences in taphonomic regimes before, during, and after the transition hinders this evaluation. Nonetheless, the demonstration of geographic and niche range changes offers a novel means of assessing the downfall of Ediacara-type taxa at the hands of emerging metazoans, which we hypothesize to be most likely due to the indirect ecological impact metazoans had upon the Ediacarans. Ultimately, the combination of studies on ecosystem construction, biostratigraphy, and biogeography showcases the magnitude of the transition at the Ediacaran–Cambrian boundary.     

Increase in Dissolved Silica of Rivers Due to a Volcanic Eruption in an Estuarine Bay (Sorsogon Bay,Philippines)

Mount Bulusan, the Philippines’ fourth most active volcano, erupted in February 21, 2011, sending volcanic ash and pyroclastic materials to its surrounding rivers. The waters drained into the estuary of harmful algal blooms plagued Sorsogon Bay. We aim to determine the impact of the 2011 volcanic eruption and the preceding volcanic ash emissions to the dissolved silica concentration of rivers draining the flanks of Mt. Bulusan and its possible implications to the phytoplankton assemblage of the bay. Six river water sampling periods from August 2010 to October 2012 overlapped with Mt. Bulusan’s active phase of volcanism. Our data shows that mean river silica from pre-eruption levels of ~?500 μM increased by more than 200% during and post-eruption. Highest Si concentration of 2270 μM was measured from Cadacan River in August 2011. Here, we argue that the sustained general increase of dissolved silica is due to the silica-containing materials from Mt. Bulusan’s eruption and that their concentration in river waters is also a function of watershed lithology and precipitation. Increase in dissolved silica and other nutrients caused a shift to diatom domination and, possibly, termination of Pyrodinium bahamense var. compressum blooms. Silica load increase in embayments is a natural process that controls the dominance of algae. Our study also highlights the importance of Philippine rivers to the global ocean silica budget as a function of high precipitation, tectonics in general, and volcanism in particular.     

TiO2 exsolution from garnet by open-system precipitation: evidence from crystallographic and shape preferred orientation of rutile inclusions

We investigated rutile needles with a clear shape preferred orientation in garnet from (ultra) high-pressure metapelites from the Kimi Complex of the Greek Rhodope by electron microprobe, electron backscatter diffraction and TEM techniques. A definite though complex crystallographic orientation relationship between the garnet host and rutile was identified in that Rt[001] is either parallel to Grt<111> or describes cones with opening angle 27.6° around Grt<111>. Each Rt[001] small circle representing a cone on the pole figure displays six maxima in the density plots. This evidence together with microchemical observations in TEM, when compared to various possible mechanisms of formation, corroborates a precipitate origin. A review of exchange vectors for Ti substitution in garnet indicates that rutile formation from garnet cannot occur in a closed system. It requires that components are exchanged between the garnet interior and the rock matrix by solid-state diffusion, a process we refer to as “open-system precipitation” (OSP). The kinetically most feasible reaction of this type will dominate the overall process. The perhaps most efficient reaction involves internal oxidation of Fe²⁺ to Fe³⁺ and transfer from the dodecahedral to the octahedral site just vacated by $ {\text{Ti}}^{ 4+ }: 6\,{\text{M}}^{ 2+ }_{ 3} {\text{TiAl}}\left[ {{\text{AlSi}}_{ 2} } \right]{\text{O}}_{ 1 2} + 6\,{\text{M}}^{ 2+ }_{ 2, 5} {\text{TiAlSi}}_{ 3} {\text{O}}_{ 1 2} = 10\,{\text{M}}^{ 2+ }_{ 3.0} {\text{Al}}_{ 1. 8} {\text{Fe}}_{0. 2} {\text{Si}}_{ 3} {\text{O}}_{ 1 2} + {\text{M}}^{2+} + 2 {\text{e}}^{-} + 1 2\,{\text{TiO}}_{ 2} . $ OSP is likely to occur at conditions where the transition of natural systems to open-system behaviour becomes apparent, as in the granulite and high-temperature eclogite facies.     

南海东沙东北部甲烷缺氧氧化作用的生物标志化合物及其碳同位素组成

南海东沙东北部碳酸盐岩和泥质沉积物中的生物标志化合物组合及其碳同位素组成分析表明,研究区内甲烷缺氧氧化作用(anaerobic oxidation of methane-AOM)发育.研究区内碳酸盐岩中含丰富的AOM标志化合物,2,6,11,15-四甲基十六烷(Crocetane-Cr.)、2,6,10,15,19-五甲基番茄烷(Pentamethylicosane-PMI)和2,6,10,15,19,23-六甲基二十四烷(Squalane-Sq角鲨烷)的13C亏损强烈(δ13C值介于-74.2‰~-119.0‰PDB之间),表明碳酸盐岩形成于AOM,同时反映该研究区曾发生过强烈、持续的富CH₄流体释放活动.柱状泥质沉积物中,AOM生物标志化合物在硫酸岩-甲烷过渡带(SMI-Sulfate-Methane Interface)边界附近相对丰度高,SMI之上样品中含量低,或未检出,表明现代环境在SMI附近有大量嗜甲烷微生物生长,使得深部上升的甲烷被大量消耗,很少有甲烷逸出海底.AOM生物标志化合物可用来指示SMI边界.不同站位、不同岩性AOM生物标志化合物组成(包括碳同位素组成)的差异反映了嗜甲烷古细菌组成的不同.     

Differential developmental toxicity of naphthoic acid isomers in medaka (Oryzias latipes) embryos

Polycyclic aromatic hydrocarbons (PAHs) are widespread persistent pollutants that readily undergo biotic and abiotic conversion to numerous transformation products in rivers, lakes and estuarine sediments. Here we characterize the developmental toxicity of four PAH transformation products each structural isomers of hydroxynaphthoic acid: 1H2NA, 2H1NA, 2H3NA, and 6H2NA. Medaka fish (Oryzias latipes) embryos and eleutheroembryos were used to determine toxicity. A 96-well micro-plate format was used to establish a robust, statistically significant platform for assessment of early life stages. Individual naphthoic acid isomers demonstrated a rank order of toxicity with 1H2NA > 2H1NA > 2H3NA > 6H2NA being more toxic. Abnormalities of circulatory system were most pronounced including pericardial edema and tube heart. To determine if HNA isomers were AhR ligands, spatial-temporal expression and activity of CYP1A was measured via in vivo EROD assessments. qPCR measurement of CYP1A induction proved different between isomers dosed at respective concentrations affecting 50% of exposed individuals (EC50s). In vitro, all ANH isomers transactivated mouse AhR using a medaka CYP1A promoter specific reporter assay. Circulatory abnormalities followed P450 induction and response was consistent with PAH toxicity. A 96-well micro-plates proved suitable as exposure chambers and provided statistically sound evaluations as well as efficient toxicity screens. Our results demonstrate the use of medaka embryos for toxicity analysis thereby achieving REACH objectives for the reduction of adult animal testing in toxicity evaluations.