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Abstract Introduction: The sea urchin Diadema mexicanum, due to its bioerosion activity, is considered of ecological importance. This phenomenon could negatively or positively affect coral reef ecosystems. The bioerosion process varies according to the abundance and size of the sea urchin. Objective: Juvenile organisms possess different metabolic needs compared to adults, so knowing their stomach content according to size allows us to quantify the selection of substrate bioeroded. Methods: To determine this, D. mexicanum individuals were collected in 12 sites from January 2009 to September 2010 along the Eastern Tropical Pacific coast. The stomach content was categorized in Carbonated Fraction (CF), Non-Carbonated Fraction (NCF), and Organic Matter (OM). Stomach content was analyzed according to a) juvenile (< 2.5 cm) or adult (> 2.5 cm) stage and b) locality. Results: Juveniles presented the following stomach content average percentages: 20.7 % OM, 12 % NCF and 67.9 % CF; and adults: 11.4 % OM, 14.8 % NCF and 73.8 % CF. Based on a Wilcoxon test and a Kendall linear regression, the following results were obtained. The carbonated fraction in the stomach increased by 0.47 units on average for every cm of growth (p < 0.05). OM consumed by D. mexicanum increases only 0.05 units for every cm of growth (p < 0.05). We found a difference of stomach content depending on the site (p < 0.05) and life stage (p < 0.05). Localities like Huatulco and Coco presented significant differences that could be related to local oceanographic conditions. Conclusions: We relate these changes of the stomach fractions to the necessity of the juvenile sea urchins for nutrients to maintain their growth. The amount of OM is crucial for the development of early stages, meaning that there is a difference in substrate selection associated with growth.

Resumen Introducción: El erizo de mar Diadema mexicanum, por su actividad de bioerosión, es considerado de importancia ecológica. Este fenómeno podría afectar negativa o positivamente a los ecosistemas de arrecifes de coral. El proceso de bioerosión varía según la abundancia y el tamaño del erizo de mar. Objetivo: Los organismos juveniles poseen diferentes necesidades metabólicas en comparación con los adultos, por lo que conocer el contenido estomacal según el tamaño, nos permite cuantificar la selección de sustrato bioerosionado. Métodos: Para determinar esto, se recolectaron individuos de D. mexicanum en 12 sitios desde enero de 2009 hasta septiembre de 2010 a lo largo de la costa del Pacífico Tropical Oriental. El contenido estomacal se clasificó en Fracción Carbonatada (FC), Fracción No Carbonatada (NCF) y Materia Orgánica (MO). El contenido estomacal se analizó según a) estadio juvenil (< 3 cm) o adulto (> 3 cm) y b) localidad. Resultados: Los juveniles presentaron los siguientes porcentajes promedio del contenido estomacal: 20.7 % OM, 12 % NCF y 67.9 % CF; y adultos: 11.4 % OM, 14.8 % NCF y 73.8 % CF. Con base en una prueba de Wilcoxon y una regresión lineal de Kendall, se obtuvieron los siguientes resultados. La fracción carbonatada en el estómago aumentó en promedio 0.47 unidades por cada cm de crecimiento (p < 0.05). La MO consumida por D. mexicanum aumenta solo 0.05 unidades por cada cm de crecimiento (p < 0.05). Encontramos una diferencia en el contenido estomacal según el sitio (p < 0.05) y el estadio de vida (P < 0.05). Localidades como Huatulco y Coco presentaron diferencias significativas que podrían estar relacionadas con las condiciones oceanográficas locales. Conclusiones: Relacionamos estos cambios de la composición porcentual del contenido estomacal con la necesidad de los erizos de mar juveniles de nutrientes para mantener su crecimiento. La cantidad de MO es crucial para el desarrollo de las primeras etapas, lo que significa que existe una diferencia en la selección de sustrato asociada con el crecimiento.

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Ionic liquids (ILs) are considered to be potential material devices for CO2 capturing and conversion to energy-adducts. They form a cage (confined-space) around the catalyst providing an ionic nano-container environment which serves as physical-chemical barrier that selectively controls the diffusion of reactants, intermediates, and products to the catalytic active sites via their hydrophobicity and contact ion pairs. Hence, the electronic properties of the catalysts in ILs can be tuned by the proper choice of the IL-cations and anions that strongly influence the residence time/diffusion of the reactants, intermediates, and products in the nano-environment. On the other hand, ILs provide driving force towards photocatalytic redox process to increase the CO2 photoreduction. By combining ILs with the semiconductor, unique solid semiconductor-liquid commodities are generated that can lower the CO2 activation energy barrier by modulating the electronic properties of the semiconductor surface. This mini-review provides a brief overview of the recent advances in IL assisted thermal conversion of CO2 to hydrocarbons, formic acid, methanol, dimethyl carbonate, and cyclic carbonates as well as its photo-conversion to solar fuels.

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In this innovative study, biogas has been associated with calcium carbonate [CaCO3] to promote the precipitation of fluorite, aiming at the treatment of wastewater with high content of fluoride. The work associates distinct sources of calcium and CO2 for the precipitation of fluorite according to previous simulation with the free software PHREEQC. Considering the reaction at equilibrium, the minimal predicted Ca dosage was 215 mg/L, lower than the 430 mg/L that was experimentally determined, independent of Ca source. The simultaneous use of CaCO3 and CO2 from distinct gas sources (pure CO2, 1:1 CO2:N2, and biogas) exhibited high performance permitting the reduction of fluoride content from 134 to 10 mg/L, with low gas consumption. The biogas consumption of 66.0 mmol/L, equivalent to 33.4 mmol/L of CO2 (1.47 kgCO2/m3treated wastewater) was predicted, indicating that the biogas storage bag of 700 L would be able to treat 469 L of wastewater. Furthermore, the inert fraction of biogas (CH4) did not impact the reaction and it may be used after the reaction as an alternative source of power, equivalent to 8.25 kWh/m3treated wastewater. Final solids were composed by fluorite and non-dissolved calcite, confirming the predictions obtained by PHREEQC.

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Bio-derived furan- and diacid-derived cyclic carbonates have been synthesized in high yields from terminal epoxides and CO2 . Furthermore, four highly substituted terpene-derived cyclic carbonates were isolated in good yields with excellent diastereoselectivity in some cases. Eleven new cyclic carbonates derived from 10-undecenoic acid under mild reaction conditions were prepared, providing the corresponding carbonate products in excellent yields. The catalyst system also performed the conversion of an epoxidized fatty acid n-pentyl ester into a cyclic carbonate under relatively mild reaction conditions (80 °C, 20 bar, 24 h). This bis(cyclic carbonate) was obtained in high yields and with different cis/trans ratios depending on the co-catalyst used. An allyl alcohol by-product was only observed as a minor product when bis(triphenylphosphine)iminium chloride was used as co-catalyst. Finally, two cyclic carbonates were used as building blocks for the preparation of non-isocyanate poly(hydroxy)urethanes by reaction with 1,4-diaminobutane.

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The martian surface has been continuously exposed to galactic cosmic radiation. Since organic compounds are degraded by ionizing radiation, knowledge of their decay constants is fundamental to predicting their stability on the martian surface. In this study, we report the radiolysis constant for the destruction of soil organic compounds at a starting concentration of ∼2011 µg C/gsoil from the Mojave Desert. The soils were exposed to gamma irradiation with absorbed doses of up to 19 MGy at room temperature, representing ∼250 million years of exposure to galactic cosmic rays. The destruction of total soil organic carbon and the formation of gases were investigated by a sequential on-line analytical array coupled to gas chromatography-mass spectrometry. Soil inorganic and organic carbon were degraded exponentially with a radiolysis constant 0.3 MGy-1(30%) producing mostly carbon dioxide (93.2%), carbon monoxide (6.2%), and methane (0.6%). Using the dose rate measured by the Radiation Assessment Detector on board the Curiosity rover, we make predictions on the survival of organic compounds in the cold martian subsurface. It is estimated that soil organic compounds with initial concentrations as those found today at the Mojave Desert would have been destroyed to levels <1 ppb at 0.1 m in depth in ∼2000 Myr. Pristine organic compounds are expected to be present at a depth of ∼1.5 m. These results are relevant for the search of organic compounds in past, present, and future missions to Mars. In particular, we predict that the upcoming ExoMars will encounter pristine organic compounds at this depth.

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Coral communities worldwide are progressively more stressed by anthropogenic activities that increase fluxes of sediment and other pollutants to nearshore areas. Some nearshore coral reef environments off the Equatorial margin of Brazil, including Pirangi and Maracajaú, Rio Grande do Norte (RN, Brazil), seem to be under human-induced stress. However, the horizontal extent of this stress, its effects, and assessment of the environmental response depend on the hydrodynamic conditions (circulation and deposition patterns), sedimentary facies, and the availability of biological indicators. We investigate two Brazilian live reefal corals' communities by examining seven photosymbiont-bearing species (PSB) of Foraminifera, Amphisorus hemprichii, Amphistegina gibbosa, Archaias angulatus, Borelis schlumbergeri, Heterostegina antillarum, Peneroplis carinatus, and Laevipeneroplis proteus, using numerical analysis FORAM Index (FI), grain size, and particulate organic and inorganic carbonate. Here, we show that coarse sand fraction followed by fine sand fraction and high hydrodynamics plays an important role in transportation and deposition of sediments and foraminiferal tests in the study area. According to FI results, conditions at Pirangi are not suitable for coral reef growth. Maracajaú has sites that are suitable for coral reef growth and sites where coral could not survive after a stress event. We need long-term assessments to improve our knowledge of the distribution and ecological importance of Brazilian reef-dwelling foraminifers and to extend the application of FI to monitoring management plans of the Pirangi and Maracajaú National Marine Parks by providing a first insight into the biodiversity patterns and a reliable tool of the reconstruction of paleo reef health.

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This study investigates the immediate and mid-term effects of the biogeochemical variables input into the Reloncaví fjord (41°40'S; 72°23'O) as a result of the eruption of Calbuco volcano. Reloncaví is an estuarine system supporting one of the largest mussels farming production within Northern Chilean-Patagonia. Field-surveys were conducted immediately after the volcanic eruption (23-30 April 2015), one month (May 2015), and five months posterior to the event (September 2015). Water samples were collected from three stations along the fjord to determine greenhouse gases [GHG: methane (CH4), nitrous oxide (N2O)], nutrients [NO3-, NO2-, PO43-, Si(OH)4, sulphate (SO42-)], and carbonate systems parameters [total pH (pHT), temperature, salinity, dissolved oxygen (O2), and total alkalinity (AT)]. Additionally, the impact of physicochemical changes in the water column on juveniles of the produced Chilean blue mussel, Mytilus chilensis, was also studied. Following the eruption, a large phytoplankton bloom led to an increase in pHT, due to the uptake of dissolved-inorganic carbon in photic waters, potentially associated with the runoff of continental soil covered in volcanic ash. Indeed, high surface SO42- and GHG were observed to be associated with river discharges. No direct evidence of the eruption was observed within the carbonate system. Notwithstanding, a vertical pattern was observed, with an undersaturation of aragonite (ΩAr < 1) both in brackish surface (<3 m) and deep waters (>10 m), and saturated values in subsurface waters (3 to 7 m). Simultaneously, juvenile mussel shells showed maximized length and weight at 4 m depth. Results suggest a localized impact of the volcanic eruption on surface GHG, nutrients and short-term effects on the carbonate system. Optimal conditions for mussel calcification were identified within a subsurface refuge in the fjord. These specific attributes can be integrated into adaptation strategies by the mussel aquaculture industry to confront ocean acidification and changing runoff conditions.

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Five metal oxides (ZnO, SnO2 , Fe2 O3 , CeO2 , La2 O3 ) were produced by the sol-gel method and tested in the direct carbonation of glycerol with CO2 . Initial tests with Fe2 O3 showed that the best reaction condition was 180 °C, 150 bar, and 12 h. The other oxides were evaluated at these conditions and were all active to the formation of glycerol carbonate. Zinc oxide was the most active catalyst, with a yield of 8.1 % in the organic carbonate. The catalytic activity decreased upon washing and drying the ZnO catalyst between the runs. Nevertheless, the activity is maintained if the ZnO is washed and calcined at 450 °C between the runs. FTIR and TGA results indicated the formation of ZnCO3 as the main cause of catalyst deactivation, which may be decomposed upon calcination of the material. No appreciable leaching of Zn was observed, indicating a truly heterogeneous catalysis.

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ABSTRACT This paper presents a sedimentological and stratigraphical study of Quaternary (Middle to Late Pleistocene/Holocene) continental carbonates outcrops inside Pantanal Basin and its surroundings, especially in Serra da Bodoquena, Pantanal do Miranda and Corumbá/Ladário plateau, in the state of Mato Grosso do Sul, as well as in Serra das Araras, in the state of Mato Grosso. The aim is to understand the depositional paleoenvironments and analyse climate and tectonic influences in their genesis and evolution. The results show that the deposition of these continental carbonates started in the Middle to Late Pleistocene and have continued, with some interruptions, until the present days. Sedimentary successions were identified in the different areas, without complete correlation. Two sedimentary successions separated by an erosional surface were described in Serra da Bodoquena and Serra das Araras. In Corumbá and Pantanal do Miranda, only one succession was described. These successions were deposited in elongated lakes parallel to fault planes; small lakes, related plains and plateaus; springs related to cliffs produced by faulting; rivers conditioned by topographic variation. The climatic interpretation, without proper temporal resolution, obtained by the stable-isotope composition and stratigraphic interpretation, indicates alternation of dry and wet periods. The Neoproterozoic faults with their neotectonics and the subsidence of the Pantanal Basin, are the major control for carbonated water flow and development of depositional areas, gradually turning plateaus into slight tilted areas, allowing the evolution of depositional systems from lakes to rivers.

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Coral reefs are among the most productive ecosystems on the planet, but are rapidly declining due to global-warming-mediated changes in the oceans. Particularly for the Caribbean region, Acropora sp. stony corals have lost ∼80% of their original coverage, resulting in vast extensions of dead coral rubble. We analyzed the microbial composition of biofilms that colonize and lithify dead Acropora palmata rubble in the Mexican Caribbean and identified the microbial assemblages that can persist under scenarios of global change, including high temperature and low pH. Lithifying biofilms have a mineral composition that includes aragonite and magnesium calcite (16 mole% MgCO(3)) and calcite, while the mineral phase corresponding to coral skeleton is basically aragonite. Microbial composition of the lithifying biofilms are different in comparison to surrounding biotopes, including a microbial mat, water column, sediments and live A. palmata microbiome. Significant shifts in biofilm composition were detected in samples incubated in mesocosms. The combined effect of low pH and increased temperature showed a strong effect after two-week incubations for biofilm composition. Findings suggest that lithifying biofilms could remain as a secondary structure on reef rubble possibly impacting the functional role of coral reefs.

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Geographic Information Systems (GIS) applications used in marine habitats are powerful tools for management and monitoring of marine reserves and resources. Here, we present a series of maps of the soft and hard substrates in the shallow waters (>80 m depth) of Parque Nacional Isla del Coco (PNIC= Isla del Coco National Park). We use bathymetry data and field data as input for a GIS, GAM, and kriging methods to generate a series of maps that describe the bottom characteristics. Eight types of bottom were found in the PNIC by composition and grain size. The shore of the island and islets consisted of rocky formations (mainly basalts), with coral reefs in the subtidal of some areas. Rhodolith beds had a dispersing distribution. The bottom on the southern and southwestern region is hard substrate, while sediments cover the northern and northeastern zones. Slightly gravelly sand dominated the bays, while gravelly sand (with more coarse grains) was frequent offshore. The inner areas of Chatham and Wafer bays have mud and organic matter. The sediments in the area are mostly carbonates, except in Bahía Yglesias where clastic sediments (from the erosion of basalts) are presented. The information generated in this study could be a valuable input for future monitoring in the PNIC.

La aplicación de Sistemas de Información Geográfica (SIG), en los hábitats marinos es muy importante para la gestión y control de las reservas y recursos marinos. Aquí se presentan una serie de mapas de los sustratos sedimentarios y duros en las aguas poco profundas (> 80 m de profundidad) del Parque Nacional Isla del Coco (PNIC). Utilizamos datos de batimetría y datos de campo como entrada para un SIG, GAM, y los métodos de “kriging” para generar una serie de mapas que describen las características del fondo. ocho tipos de fondo marino se encuentran en el PNIC. La orilla de la isla y los islotes consistía de formaciones rocosas (principalmente basaltos), con arrecifes de coral en el submareal de algunas áreas. Las camas de rodolitos tienen una distribución dispersa. El fondo al sur y suroeste es dominado por sustratos duros, mientras que en el norte y noreste, principalmente por los sustratos sedimentarios. La arena algo gravosa dominó en las bahías, mientras que la arena gravosa lo fue fuera de la costa. Sólo en dos puntos, las zonas interiores de las bahías de Chatham y Wafer, se tiene la presencia de barro y mayor materia orgánica. Los sedimentos fueron altos en contenido de carbonatos, principalmente de color claro, pero en Bahía Yglesias el sedimento era oscuro, por ser arena volcánica producto de la erosión de los basaltos. Los mapas elaborados a partir del presente estudio pueden ser utilizados para el seguimiento futuro de los recursos marinos en PNIC.

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The late Cambrian - late Tremadocian La Silla Formation is a carbonate unit of the eastern Precordillera in Argentina whose facies indicate a shallow platform environment. Until this moment, there were no studies that referred to the diagenetic evolution of these rocks. The present study involves the characteristics and distribution of the silicification that affects this unit and determines its different diagenetic stages through petrographic (with cathodoluminescence support) and stratigraphic analyses. An early diagenetic chert, in a stage previous to the compactation, was observed. This chert is related to silica-rich seawater in contact with permeable and porous sediments. A later pulse of chert, associated with fracturing, also occurs. The knowledge provided by the characteristics and distribution of chert in these carbonates is significant, especially when considering that the La Silla Formation in San Juan province is the most quarried unit for the elaboration of lime.

A Formação La Silla (Neo Cambriano-Neo Tremadociano) é formada por depósitos carbonáticos da região da Pré-Cordilheira leste, Argentina. As faciologias encontradas em tais depósitos indicam um ambiente de deposição caracterizado por uma plataforma rasa. Até o momento, nenhum estudo tratou especificamente da evolução diagenética dessas rochas. O presente estudo envolve as características e distribuição da silicificação que afeta esta formação e apresenta os diferentes estágios diagenéticos ocorridos, através de análises petrográficas (auxiliadas por catodoluminescência) e estratigráficas. Foi identificado um pulso precoce de silicificação, anterior ao processo de compactação das rochas afetadas. Esta silicificação foi favorecida pela presença de água do mar rica em sílica em contato com sedimentos porosos e permeáveis. Também foi identificado um pulso de silicificação tardia, associado a eventos de fraturamento das rochas. O conhecimento adquirido sobre as características e a distribuição da silicificação nestes depósitos carbonáticos é importante, especialmente quando se considera que a Formação La Silla, na Província de San Juan, é a formação mais minerada para a produção de calcário.