Phenological Changes of Blooming Diatoms Promoted by Compound Bottom-Up and Top-Down Controls

Understanding phytoplankton species-specific responses to multiple biotic and abiotic stressors is fundamental to assess phenological and structural shifts at the community level. Here, we present the case of Thalassiosira curviseriata, a winter-blooming diatom in the Bahía Blanca Estuary, Argentina, which displayed a noticeable decrease in the past decade along with conspicuous changes in phenology. We compiled interannual field data to assess compound effects of environmental variations and grazing by the invasive copepod Eurytemora americana. The two species displayed opposite trends over the period examined. The diatom decreased toward the last years, mainly during the winters, and remained relatively constant over the other seasons, while the copepod increased toward the last years, with an occurrence restricted to winter and early spring. A quantitative assessment by structural equation modeling unveiled that the observed long-term trend of T. curviseriata resulted from the synergistic effects of environmental changes driven by water temperature, salinity, and grazing. These results suggest that the shift in the abundance distribution of T. curviseriata toward higher annual ranges of temperature and salinity—as displayed by habitat association curves—constitutes a functional response to avoid seasonal overlapping with its predator in late winters. The observed changes in the timing and abundance of the blooming species resulted in conspicuous shifts in primary production pulses. Our results provide insights on mechanistic processes shaping the phenology and structure of phytoplankton blooms.     

Sulfate Reduction and Sulfur Cycles at Two Seagrass Beds Inhabited by Cold Affinity <Emphasis Type="Italic">Zostera marina</Emphasis> and Warm Affinity <Emphasis Type="Italic">Halophila nipponica</Emphasis> in Temperate Coastal Waters

To evaluate the impact of invading seagrass on biogeochemical processes associated with sulfur cycles, we investigated the geochemical properties and sulfate reduction rates (SRRs) in sediments inhabited by invasive warm affinity Halophila nipponica and indigenous cold affinity Zostera marina. A more positive relationship between SRR and below-ground biomass (BGB) was observed at the H. nipponica bed (SRR = 0.6809 × BGB ? 4.3162, r ² = 0.9878, p = 0.0006) than at the Z. marina bed (SRR = 0.3470 × BGB ? 4.0341, r ² = 0.7082, p = 0.0357). These results suggested that SR was more stimulated by the dissolved organic carbon (DOC) exuded from the roots of H. nipponica than by the DOC released from the roots of Z. marina. Despite the enhanced SR in spring-summer, the relatively lower proportion (average, 20%) of acid-volatile sulfur (AVS) in total reduced sulfur and the strong correlation between total oxalate-extractable Fe (Fe_(oxal)) and chromium-reducible sulfur (CRS = 0.2321 × total Fe_(oxal) + 1.8180, r ² = 0.3344, p = 0.0076) in the sediments suggested the rapid re-oxidation of sulfide and precipitation of sulfide with Fe. The turnover rate of the AVS at the H. nipponica bed (0.13 day^?1) was 2.5 times lower than that at the Z. marina bed (0.33 day^?1). Together with lower AVS turnover, the stronger correlation of SRR to BGB in the H. nipponica bed suggests that the extension of H. nipponica resulting from the warming of seawater might provoke more sulfide accumulation in coastal sediments.     

System dynamic modeling to assess the effect of subsurface drain spacing and depth on minimizing the environmental impacts

The excessive loss of soil nitrogen through drainage losses causes different environmental problems. The depth and spacing drain of drains play an important role in the quality and quantity of discharged drainage into the environment. In this paper, a simple but comprehensive model using system dynamic approach for water cycle and nitrogen dynamics was used to simulate the effect of drain depth and spacing on nitrate and ammonium losses in a sugarcane agro-industrial company. Twenty-four scenarios were modeled including the combination of four different drain depths and six drain spacing to compare the effect of drain depth and spacing on the nitrogen uptake by plant, denitrification, net mineralization, the amount of ammonium losses through runoff, nitrate and ammonium losses through drainage water, the sum of excessive water, the stress day index and the relative yield. The results indicated that optimal drainage system density is obtained in the depth of 1.1 m and spacing of 80 m, in a way that the total drainage losses would be reduced up to an acceptable level. The optimum designing of the drainage systems according to environmental criteria can control nitrogen pollution load at farm level and can therefore have appropriate results both in terms of economic and environmental considerations.     

Evaluating the production and bio-stimulating effect of 5-methyl 1, hydroxy phenazine on microbial fuel cell performance

The role of endogenous redox mediators has considerable importance in electron shuttling reactions and associated performance of microbial fuel cell. Single-chamber microbial fuel cell-II with dual air-cathode assembly (area = 18.84 cm²) supported highest bacterial (Pseudomonas aeruginosa) density (6.7 × 10⁹) and active biomass [4.4 ± 0.3 mg cm^?2 (carbon content = 0.48 ± 0.1 mg cm^?2)] on anode thereby resulting in maximum production of redox metabolite, 5-methyl 1, hydroxy phenazine (301 ppm) and voltage (595 ± 5 mV) than similar cells with relatively less surface area of cathode. It was further revealed that 5-methyl 1, hydroxy phenazine production was positively correlated with chemical oxygen demand removal rate (77 ± 2.5%) and power generation (66.6 ± 2.2 mW cm^?2) efficiency of single-chamber microbial fuel cell-II. Maximum power density of 258 ± 4.5 mW cm^?2 was generated when reactor was supplemented with 2 ml crude extract of 5-methyl 1, hydroxy phenazine metabolite, whereas power output was about 229 ± 2.5 mW cm^?2 when reactor was bio-stimulated with 1 ml pure extract of 5-methyl 1, hydroxy phenazine. With this concentration, the electrochemical response of mixed culture biofilm (sediment) was enhanced by 99.3%. However, further increase in concentration of endogenous mediator proved to be limiting on reactor performance. Pyrosequencing and phylogenetic analysis on the basis of partial 16S rRNA sequences demonstrated both culturable and unculturable bacterial species in anodic biofilm and relative abundance of family Pseudomonadaceae was found to be maximum, i.e., 61.7% followed by Rhodocyclaceae 19.2%, Xanthomonadaceae 6.3% and Opitutaceae 3.18%.     

THERIA_G: a software program to numerically model prograde garnet growth

We present the software program THERIA_G, which allows for numerical simulation of garnet growth in a given volume of rock along any pressure–temperature–time (P–T–t) path. THERIA_G assumes thermodynamic equilibrium between the garnet rim and the rock matrix during growth and accounts for component fractionation associated with garnet formation as well as for intracrystalline diffusion within garnet. In addition, THERIA_G keeps track of changes in the equilibrium phase relations, which occur during garnet growth along the specified P–T–t trajectory. This is accomplished by the combination of two major modules: a Gibbs free energy minimization routine is used to calculate equilibrium phase relations including the volume and composition of successive garnet growth increments as P and T and the effective bulk rock composition change. With the second module intragranular multi-component diffusion is modelled for spherical garnet geometry. THERIA_G allows to simulate the formation of an entire garnet population, the nucleation and growth history of which is specified via the garnet crystal size frequency distribution. Garnet growth simulations with THERIA_G produce compositional profiles for the garnet porphyroblasts of each size class of a population and full information on equilibrium phase assemblages for any point along the specified P–T–t trajectory. The results of garnet growth simulation can be used to infer the P–T–t path of metamorphism from the chemical zoning of garnet porphyroblasts. With a hypothetical example of garnet growth in a pelitic rock we demonstrate that it is essential for the interpretation of the chemical zoning of garnet to account for the combined effects of the thermodynamic conditions of garnet growth, the nucleation history and intracrystalline diffusion. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

Chemical composition,volatile components,and trace elements in melts of the Karymskii volcanic center,Kamchatka, and Golovnina volcano,Kunashir Island: Evidence from inclusions in minerals

Melt inclusions were examined in phenocrysts in basalt, andesite, dacite, and rhyodacite from the Karymskii volcanic center in Kamchatka and dacite form Golovnina volcano in Kunashir Island, Kuriles. The inclusions were examined by homogenization and by analyzing glasses in more than 80 inclusions on an electron microscope and ion microprobe. The SiO₂ concentrations in the melt inclusions in plagioclase phenocrysts from basalts from the Karymskii volcanic center vary from 47.4 to 57.1 wt %, these values for inclusions in plagioclase phenocrysts from andesites are 55.7–67.1 wt %, in plagioclase phenocrysts from the dacites and rhyodacites are 65.9–73.1 wt %, and those in quartz in the rhyodacites are 72.2–75.7 wt %. The SiO₂ concentrations in melt inclusions in quartz from dacites from Golovnina volcano range from 70.2 to 77.0 wt %. The basaltic melts are characterized by usual concentrations of major components (wt %): TiO₂ = 0.7–1.3, FeO = 6.8–11.4, MgO = 2.3–6.1, CaO = 6.7–10.8, and K₂O = 0.4–1.7; but these rocks are notably enriched in Na₂O (2.9–7.4 wt % at an average of 5.1 wt %, with the highest Na₂O concentration detected in the most basic melts: SiO₂ = 47.4–52.0 wt %. The concentrations of volatiles in the basic melts are 1.6 wt % for H₂O, 0.14 wt % for S, 0.09 wt % for Cl, and 50 ppm for F. The andesite melts are characterized by high concentrations (wt %) of FeO (6.5 on average), CaO (5.2), and Cl (0.26) at usual concentrations of Na₂O (4.5), K₂O (2.1), and S (0.07). High water concentrations were determined in the dacite and rhyodacite melts: from 0.9 to 7.3 wt % (average of 15 analyses equals 4.5 wt %). The Cl concentration in these melts is 0.15 wt %, and those of F and S are 0.06 and 0.01 wt %, respectively. Melt inclusions in quartz from the dacites of Golovnina volcano are also rich in water: they contain from 5.0 to 6.7 wt % (average 5.6 wt %). The comparison of melt compositions from the Karymskii volcanic center and previously studied melts from Bezymyannyi and Shiveluch volcanoes revealed their significant differences. The former are more basic, are enriched in Ti, Fe, Mg, Ca, Na, and P but significantly depleted in K. The melts of the Karymskii volcanic center are most probably less differentiated than the melts of Bezymyannyi and Shiveluch volcanoes. The concentrations of water and 20 trace elements were measured in the glasses of 22 melt inclusions in plagioclase and quartz from our samples. Unusually high values were obtained for Li concentrations (along with high Na concentrations) in the basaltic melts from the Karymskii volcanic center: from 118 to 1750 ppm, whereas the dacite and rhyolite melts contain 25 ppm Li on average. The rhyolite melts of Golovnina volcano are much poorer in Li: 1.4 ppm on average. The melts of the Karymskii volcanic center are characterized by relative minima at Nb and Ti and maxima at B and K, as is typical of arc magmas.     

The Meso-Cenozoic thermo-tectonic evolution of the Eastern Pyrenees: an <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar fission track and (U–Th)/He thermochronological study of the Canigou and Mont-Louis massifs

Vertical displacements on the SW–NE Têt fault (Eastern Pyrenees Axial Zone, France), which separates the Variscan Canigou-Carança and Mont-Louis massifs, were constrained using a thermochronologic multi-method approach. ⁴⁰Ar/³⁹Ar data from the granitic Mont-Louis massif record its Variscan cooling history and reveal no ages younger than Early Cretaceous, while the Canigou-Carança gneiss massif records systematically younger ⁴⁰Ar/³⁹Ar ages. These younger ⁴⁰Ar/³⁹Ar ages in the Canigou-Carança gneiss massif are the result of partial to total rejuvenation of argon isotopic systems related to a thermal flow coeval with the Cretaceous HT-BP metamorphism in the North Pyrenean Zone. Only the deepest rocks from the Canigou-Carança suffered this extensive Mid-Cretaceous thermal overprint probably due to differential burial around 4 km at that time. The post Mid-Cretaceous vertical displacements along the Têt fault are recorded by “low” temperature thermochronology using K-feldspar ⁴⁰Ar/³⁹Ar, zircon and apatite fission track and (U–Th)/He datings. The Mont-Louis granite samples experienced a long period of protracted cooling reflecting a lack of thermo-tectonic activity in this area from Late Palaeozoic to Early Cenozoic, followed by cooling from 55–60 Ma to Late Eocene at a mean rate of 15–20°C/Ma in the final stage. This cooling stage corresponds to Têt fault reactivation with a reversed component, promoting exhumation of the Mont-Louis roof zone contemporaneously with the south-vergent Pyrenean thrusting. In the Canigou-Carança massif, the main cooling event occurred from 32 to 18 Ma at a maximum rate of 30°C/Ma during Early Oligocene followed by a more moderate rate of 3°C/Ma from Late Oligocene to Early Burdigalian, coeval with the normal reactivation of the Têt fault in brittle conditions that accommodated the final exhumation of the massif during the opening of the Gulf of Lion.     

Simulation of the molecular mass distributions of Si anions on the liquidus of the Na<Subscript>2</Subscript>O-SiO<Subscript>2</Subscript> system with regard for the disproportionation of <Emphasis Type="Italic">Q</Emphasis> structons

A new version of the STRUCTON (2009) computer model is proposed for the simulation of the molecular mass distributions (MMD) characterizing the diversity of anions in silicate melts depending on their polymerization and temperature. In contrast to earlier versions, the new version of the model accounts for disproportionation reactions of Q ⁿ species and makes use of their proportions in the statistical simulations of the origin of real Si-O complexes. The new potentialities of the STRUCTON program package are illustrated by its application to studying the structural-chemical characteristics of melts in the Na₂O-SiO₂ system along its liquidus line, including the points of eutectics and phase transitions at 0.333 ≤ $ N_{SiO_2 } $ N_{SiO_2 } < 0.500. This problem is solved with the use of a temperature-composition dependence of polymerization constants K _p ^Na in the Toop-Samis approximation. The variations in K _p ^Na were proved to be as large as three orders of magnitude due to both the temperature effect at a constant composition and the composition effect at a constant temperature. The results of the MMD simulations on the liquidus show that the concentration of the SiO₄⁴⁻ ion strongly decreases, and the proportion of chain species increases compared to those at a stochastic distribution. The concentration of the Si₂O₇⁶⁻ anion reaches its maximum (∼42%) at 40 mol % in the liquid, i.e., the composition of Na₆Si₂O₇. At $ N_{SiO_2 } $ N_{SiO_2 } > 0.40, this ion dominates over the SiO₄⁴⁻ monomer. More silicic melts with $ N_{SiO_2 } $ N_{SiO_2 } ≥ 0.45, are dominated by (Si _n O_3n )³ⁿ⁻ ring species, and the concentrations of these species are related as (Si₃O₉)⁶⁻ > (Si₄O₁₂)⁸⁻ > (Si₅O₁₅)¹⁰⁻. The maximum concentration of these flat rings also occurs near the composition of stoichiometric metasilicate with Si/O = 0.333. The comparison of the dependence of the average size of anions i _av and the average number of their species on depolymerization indicates that a change in the proportion of Q ⁿ species in melt at decreasing temperature results in structural restyling and an increase in the average size of Si-O complexes. The average number of anion species thereby decreases compared to that in a stochastic MMD. The results presented in this publication direct the progress in the thermodynamic theory of silicate melts to a new avenue that makes use of the capabilities and advantages of the ion-polymer model, the theory of associated solutions, spectroscopic data, and the experimental study of variations in oxide activities depending on composition and temperature.     

Catagenesis and burial metamorphism of terrigenous and volcanic sequences (section recovered by the En-Yakhinskaya parametric borehole SG-7)

Secondary alterations of Cretaceous, Jurassic, and Triassic terrigenous complexes recovered by borehole SG-7 were studied from the depth of 3620 m to 6920 m (roof of basalts). Down to the depth of ∼6770 m, the section shows a gradual intensification of catagenetic alterations of sandy rocks: the formation of pressure dissolution textures and regeneration of clastic quartz. Intensification of the transformation of clay minerals is not observed in this mineral. Variations in the contents of illite, hydromicas, mixed-layer minerals, smectite, chlorite, and kaolinite at different depths of the recovered section are related to changes in the provenance during the accumulation of sedimentary complexes. The Middle Triassic coarse-grained sandy rocks (suprabasalt sequence) are more intensely transformed: they are marked by microstylolitic textures of pressure dissolution, recrystallization blastesis of clastic quartz grains, and newly formed zoisite. The composition of clay minerals is also characterized by variation: micas are represented by sericite with ΔD = 0; Fe-chlorite and kaolinite are noted. These features suggest the absence of linear positive correlation of T and P with the subsidence depth of sedimentary complexes. Intense heating (up to 200–300°C) of the Middle Triassic suprabasalt rocks is likely caused by trap activity (intense effusion of basalt lavas). Investigation of secondary minerals in basalts recovered by borehole SG-7 revealed that the grade of their transformation matches the medium-temperature subfacies of the greenschist facies.