Seawater carbonate chemistry and processes during experiments with coccolithophores (Emiliania huxleyi and Gephyrocapsa oceanica), 2000

The formation of calcareous skeletons by marine planktonic organisms and their subsequent sinking to depth generates a continuous rain of calcium carbonate to the deep ocean and underlying sediments1. This is important in regulating marine carbon cycling and ocean-atmosphere CO2 exchange2. The present rise in atmospheric CO2 levels3 causes significant changes in surface ocean pH and carbonate chemistry4. Such changes have been shown to slow down calcification in corals and coralline macroalgae5,6, but the majority of marine calcification occurs in planktonic organisms. Here we report reduced calcite production at increased CO2 concentrations in monospecific cultures of two dominant marine calcifying phytoplankton species, the coccolithophorids Emiliania huxleyi and Gephyrocapsa oceanica . This was accompanied by an increased proportion of malformed coccoliths and incomplete coccospheres. Diminished calcification led to a reduction in the ratio of calcite precipitation to organic matter production. Similar results were obtained in incubations of natural plankton assemblages from the north Pacific ocean when exposed to experimentally elevated CO2 levels. We suggest that the progressive increase in atmospheric CO2 concentrations may therefore slow down the production of calcium carbonate in the surface ocean. As the process of calcification releases CO2 to the atmosphere, the response observed here could potentially act as a negative feedback on atmospheric CO2 levels.

Echinometra sea urchins acclimatised to elevated pCO2 at volcanic vents outperform those under present-day pCO2 conditions

Rising atmospheric CO2 concentrations will significantly reduce ocean pH during the 21st century (ocean acidification, OA). This may hamper calcification in marine organisms such as corals and echinoderms, as shown in many laboratory-based experiments. Sea urchins are considered highly vulnerable to OA. We studied an Echinometra species on natural volcanic CO2 vents in Papua New Guinea, where they are CO2-acclimatized and also subjected to secondary ecological changes from elevated CO2. Near the vent site, the urchins experienced large daily variations in pH (> 1 unit) and pCO2 (> 2000 ppm) and average pH values (pHT 7.73) much below those expected under the most pessimistic future emission scenarios. Growth was measured over a 17-month period using tetracycline tagging of the calcareous feeding lanterns. Average-sized urchins grew more than twice as fast at the vent compared with those at an adjacent control site, and assumed larger sizes at the vent compared to the control site and two other sites at another reef near-by. A small reduction in gonad weight was detected at the vents, but no differences in mortality, respiration, or degree of test calcification were detected between urchins from vent and control populations. Thus, urchins did not only persist but actually 'thrived' under extreme CO2 conditions. We suggest an ecological basis for this response: increased algal productivity under increased pCO2 provided more food at the vent, resulting in higher growth rates. The wider implication of our observation is that laboratory studies on non-acclimatized specimens, which typically do not consider ecological changes, can lead to erroneous conclusions on responses to global change.

Adaptive evolution of a key phytoplankton species to ocean acidification

Ocean acidification, the drop in seawater pH associated with the ongoing enrichment of marine waters with carbon dioxide from fossil fuel burning, may seriously impair marine calcifying organisms. Our present understanding of the sensitivity of marine life to ocean acidification is based primarily on short-term experiments, in which organisms are exposed to increased concentrations of CO2. However, phytoplankton species with short generation times, in particular, may be able to respond to environmental alterations through adaptive evolution. Here, we examine the ability of the world's single most important calcifying organism, the coccolithophore Emiliania huxleyi, to evolve in response to ocean acidification in two 500-generation selection experiments. Specifically, we exposed E. huxleyi populations founded by single or multiple clones to increased concentrations of CO2. Around 500 asexual generations later we assessed their fitness. Compared with populations kept at ambient CO2 partial pressure, those selected at increased partial pressure exhibited higher growth rates, in both the single- and multiclone experiment, when tested under ocean acidification conditions. Calcification was partly restored: rates were lower under increased CO2 conditions in all cultures, but were up to 50% higher in adapted compared with non-adapted cultures. We suggest that contemporary evolution could help to maintain the functionality of microbial processes at the base of marine food webs in the face of global change.

Otimização de parâmetros mecânicos e microestruturais dos moldes em areia de sílica ligados quimicamente pelo processo de cura a frio em fundição de aço

Surface defects on steel parts borne costs of smelting industries due to the need of rework. Sand molds are frequently used in foundry industries and largely responsible for providing surface defects. This study aims to optimize the levels of the molding process variables to minimize the occurrence of surface defects in steel castings in silica sand molds chemically linked by cold cure process. The methodology used the experimental design with split plot, being considered in the study the resin percentage factors in the mold formulation, addition of iron oxide, type of paint, the paint application method, amount of ink layers, use of hot air along the lines and waiting time of the mold before casting. They were analyzed as response variables erosion defects, sand inclusion, penetration, porosity and surface finish. Tensile strength tests were performed to evaluate the influence of factors on mechanical parameters and the microstructural parameters were carried out the analysis of X-ray diffraction, scanning electron microscopy (SEM) and thermal analysis (TG / DSC / dilatometry). The results elucidate that for the faulty erosion, the only significant factor with a 95% confidence level was the type of ink and the ink alumina-based superior results obtained. For the sand inclusion of defect, there were three significant factors, with best results obtained with alumina-based paint and spray applied using hot air in the mold before casting the metal. For the defect penetration, there were four significant factors, the best results being achieved with 0.8% of resin and addition of iron oxide in the molding formulation, the paint being applied by brush and standby time of 24 hours before leak. For the defect porosity with a 95% confidence level, no significant factors. For the defect surface finish, the best results were achieved with the 0.8% formulation of the resin in the mold and application of the paint brush. To obtain the levels of the factors that optimize all defects simultaneously, we performed a weighted average of the results of each type of fault, concluding that the best levels of the factors were: 0.8% resin and addition of iron oxide in the formulation of the template, application of two coats of paint applied with a brush or spray, using hot air in the mold before casting and 24 hours of waiting ready the mold before casting. These levels of the optimized factors were used in an experiment to confirm that ratified the results, helping to reduce rework and consequently reducing costs of cast steel parts.

Seawater carbonate chemistry and biological processes during experiments with four species of marine diatoms

The effect of pCO2 on carbon acquisition and intracellular assimilation was investigated in the three bloom-forming diatom species, Eucampia zodiacus (Ehrenberg), Skeletonema costatum (Greville) Cleve, Thalassionema nitzschioides (Grunow) Mereschkowsky and the non-bloom-forming Thalassiosira pseudonana (Hust.) Hasle and Heimdal. In vivo activities of carbonic anhydrase (CA), photosynthetic O2 evolution, CO2 and HCO3? uptake rates were measured by membrane-inlet mass spectrometry (MIMS) in cells acclimated to pCO2 levels of 370 and 800 ?atm. To investigate whether the cells operate a C4-like pathway, activities of ribulose-1,5-bisphosphate carboxylase (RubisCO) and phosphoenolpyruvate carboxylase (PEPC) were measured at the mentioned pCO2 levels and a lower pCO2 level of 50 ?atm. In the bloom-forming species, extracellular CA activities strongly increased with decreasing CO2 supply while constantly low activities were obtained for T. pseudonana. Half-saturation concentrations (K1/2) for photosynthetic O2 evolution decreased with decreasing CO2 supply in the two bloom-forming species S. costatum and T. nitzschioides, but not in T. pseudonana and E. zodiacus. With the exception of S. costatum, maximum rates (Vmax) of photosynthesis remained constant in all investigated diatom species. Independent of the pCO2 level, PEPC activities were significantly lower than those for RubisCO, averaging generally less than 3%. All examined diatom species operate highly efficient CCMs under ambient and high pCO2, but differ strongly in the degree of regulation of individual components of the CCM such as Ci uptake kinetics and extracellular CA activities. The present data do not suggest C4 metabolism in the investigated species.

Alterações fisiológicas causadas por fungicidas em soja infectada naturalmente por oídio

Soybean crop is substantially important for both Brazilian and international markets. A relevant disease that affects soybeans is powdery mildew, caused by fungus Erysiphe diffusa. The objective of this master’s thesis was to analyze physiological changes produced by fungicides in two greenhouse-grown soybean genotypes (i.e., Anta 8500 RR and BRS Santa Cruz RR) naturally infected with powdery mildew. A complete randomized block design was used with six replications in a 2x5 factorial arrangement. Treatments consisted of applications of Azoxystrobin, Biofac (fermented solution of Penicillium sp.), Carbendazim or Picoxystrobin fungicides, and a Control (no fungicide application). Three applications were performed in the experimental period, and each eventually represented a period of data collection. Gas exchanges, chlorophyll content, fluorescence of chlorophyll a and disease severity were measured twice a week. Dry grain mass production was measured at the end of the experiment. Areas under progression curve of variables were submitted to both ANOVA and Tukey’s test at 5% significance. Treatments Azoxystrobin, Biofac and Picoxystrobin had higher photosynthetic rates than Control in the second period, with genotype Anta having higher rate than Santa Cruz. Biofac had higher transpiration rate than Control in the second period, while Biofac and Picoxystrobin had higher figures in Santa Cruz in the third period. Carbendazim had greater stomatal conductance in Anta, whilst Azoxystrobin, Biofac and Picoxystrobin had greater values than Carbendazim in Santa Cruz. Biofac and Picoxystrobin had greater intercellular CO2 concentration in Santa Cruz. Azoxystrobin and Picoxystrobin had greater instantaneous water use efficiency than Control, with Anta being more efficient than Santa Cruz. Biofac and Picoxystrobin had greater intrinsic water use efficiency in Anta, while Carbendazim increased efficiency in Santa Cruz. Azoxystrobin, Biofac and Picoxystrobin had greater carboxylation efficiency than Control in the second period, with Anta being more efficient than Santa Cruz. Azoxystrobin and Biofac had greater contents of chlorophylls a, b and a+b than Control in the second period. Azoxystrobin had greater effective quantum yield than Control and Picoxystrobin. All treatments faced increasing disease severity over time, with Anta being less resistant than Santa Cruz. As for production, data showed that: (1) Santa Cruz was more productive than Anta, having the greatest dry grain mass with Carbendazim, and (2) Anta’s lower disease severity did not translate into higher productions. In conclusion, strobilurins (Azoxystrobin and Picoxystrobin) and Biofac performed similarly as to their physiological effects on soybeans; however, these effects did not lead to increased dry grain mass by the end of the experiment.

(Table 3) Reduced inorganic sulphur, d34S and nickel content of ODP Leg 165 sites

Leg 165 of the Ocean Drilling Program afforded a unique opportunity to investigate organic and inorganic geochemistry across a wide gradient of sediment compositions and corresponding chemical pathways. The solid fractions at Sites 998, 999, 1000, and 1001 reveal varying proportions of reactive carbonate species, a labile volcanic ash fraction occurring in discrete layers and as a dispersed component, and detrital fluxes that derive from continental weathering. The relative proportions and reactivities of these end-members strongly dictate the character of the diagenetic profiles observed during the pore-water work of Leg 165. In addition, alteration of the well-characterized basaltic basement at Site 1001 has provided a strong signal that is reflected in many of the dissolved components. The relative effects of basement alteration and diagenesis within the sediment column are discussed in terms of downcore relationships for dissolved calcium and magnesium. With the exception of Site 1002 in the Cariaco Basin, the sediments encountered during Leg 165 were uniformly deficient in organic carbon (typically <0.1 wt%). Consequently, rates of organic oxidation were generally low and dominated by suboxic pathways with subordinate levels of bacterial sulfate reduction and methanogenesis. The low rates of organic remineralization are supported by modeled rates of sulfate reduction. Site 1000 provided an exception to the generally low levels of microbially mediated redox cycling. At this site the sediment is slightly more enriched in organic phases, and externally derived thermogenic hydrocarbons appear to aid in driving enhanced levels of redox diagenesis at great depths below the seafloor. The entrapment of these volatiles corresponds with a permeability seal defined by a pronounced Miocene minimum in calcium carbonate concentration recognized throughout the basin and with a dramatic downcore increase in the magnitude of limestone lithification. The latter has been tentatively linked to increases in alkalinity associated with microbial oxidation of organic matter and gaseous hydrocarbons. Recognition and quantification of previously unconstrained large volumes and frequencies of Eocene and Miocene silicic volcanic ash within the Caribbean Basin is one of the major findings of Leg 165. High frequencies of volcanic ash layers manifest as varied but often dominant controls on pore-water chemistry. Sulfur isotope results are presented that speak to secondary metal and sulfur enrichments observed in ash layers sampled during Leg 165. Ultimately, a better mechanistic understanding of these processes and the extent to which they have varied spatially and temporally may bear on the global mass balances for a range of major and minor dissolved components of seawater.

Table 1. pH, Temperature, conductivity and hydrochemistry of samples

Carbon dioxide deep geological storage, especially in deep saline aquifers, is one of the preferred technological options to mitigate the effects of greenhouse gases emissions. Thus, in the last decade, studies characterising the behaviour of potential CO2 deep geological storage sites along with thorough safety assessments have been considered essential in order to minimise the risks associated with these sites. The study of natural analogues represents the best source of reliable information about the expected hydrogeochemical processes involved in the CO2 storage in such deep saline aquifers. In this work, a comprehensive study of the hydrogeochemical features and processes taking place at the natural analogue of the Alicún de las Torres thermal system (Betic Cordillera) has been conducted. Thus, the main water/CO2/rock interaction processes occurring at the thermal system have been identified, quantified and modelled, and a principle conclusion is that the hydrogeochemical evolution of the thermal system is controlled by a global dedolomitization process triggered by gypsum dissolution. This geochemical process generates a different geochemical environment to that which would result from the exclusive dissolution of carbonates from the deep aquifer, which is generally considered as the direct result of CO2 injection in a deep carbonate aquifer. Therefore, discounting of the dedolomitization process in any CO2 deep geological storage may lead to erroneous conclusions. This process will also influence the porosity evolution of the CO2 storage formation, which is a very relevant parameter when evaluating a reservoir for CO2 storage. The geothermometric calculation performed in this work leads to estimate that the thermal water reservoir is located between 650 and 800 m depth, which is very close to the minimum required to inject CO2 in a deep geological storage. It is clear that the proper characterisation of the features and hydrogeochemical processes taking place at a natural system analogous to a man-made deep geological storage will provide useful conceptual, semi-quantitative and even quantitative information about the processes and consequences that may occur at the artificial storage system.

Seawater carbonate chemistry and brown dottyback (Pseudochromis fuscus) movement and feeding behaviour during experiments, 2011

Changes in olfactory-mediated behaviour caused by elevated CO2 levels in the ocean could affect recruitment to reef fish populations because larval fish become more vulnerable to predation. However, it is currently unclear how elevated CO2 will impact the other key part of the predator-prey interaction - the predators. We investigated the effects of elevated CO2 and reduced pH on olfactory preferences, activity levels and feeding behaviour of a common coral reef meso-predator, the brown dottyback (Pseudochromis fuscus). Predators were exposed to either current-day CO2 levels or one of two elevated CO2 levels (~600 µatm or ~950 µatm) that may occur by 2100 according to climate change predictions. Exposure to elevated CO2 and reduced pH caused a shift from preference to avoidance of the smell of injured prey, with CO2treated predators spending approximately 20% less time in a water stream containing prey odour compared with controls. Furthermore, activity levels of fish was higher in the high CO2 treatment and feeding activity was lower for fish in the mid CO2treatment; indicating that future conditions may potentially reduce the ability of the fish to respond rapidly to fluctuations in food availability. Elevated activity levels of predators in the high CO2 treatment, however, may compensate for reduced olfactory ability, as greater movement facilitated visual detection of food. Our findings show that, at least for the species tested to date, both parties in the predator-prey relationship may be affected by ocean acidification. Although impairment of olfactory-mediated behaviour of predators might reduce the risk of predation for larval fishes, the magnitude of the observed effects of elevated CO2 acidification appear to be more dramatic for prey compared to predators. Thus, it is unlikely that the altered behaviour of predators is sufficient to fully compensate for the effects of ocean acidification on prey mortality.

Seawater carbonate chemistry and settlement of a spawning coral on three common species of crustose coralline algae

Concern about the impacts of ocean acidification (OA) on ecosystem function has prompted many studies to focus on larval recruitment, demonstrating declines in settlement and early growth at elevated CO2 concentrations. Since larval settlement is often driven by particular cues governed by crustose coralline algae (CCA), it is important to determine whether OA reduces larval recruitment with specific CCA and the generality of any effects. We tested the effect of elevated CO2 on the survival and settlement of larvae from the common spawning coral Acropora selago with 3 ecologically important species of CCA, Porolithon onkodes, Sporolithon sp., and Titanoderma sp. After 3 d in no-choice laboratory assays at 447, 705, and 1214 µatm pCO2, the rates of coral settlement declined as pCO2 increased with all CCA taxa. The magnitude of the effect was highest with Titanoderma sp., decreasing by 87% from the ambient to highest CO2 treatment. In general, there were high rates of larval mortality, which were greater with the P. onkodes and Sporolithon sp. treatments (~80%) compared to the Titanoderma sp. treatment (65%). There was an increase in larval mortality as pCO2 increased, but this was variable among the CCA species. It appears that OA reduces coral settlement by rapidly altering the chemical cues associated with the CCA thalli and microbial community, and potentially by directly affecting larval viability.

Interactive effects of ocean acidification and nitrogen limitation on the diatom Phaeodactylum tricornutum

Climate change is expected to bring about alterations in the marine physical and chemical environment that will induce changes in the concentration of dissolved CO2 and in nutrient availability. These in turn are expected to affect the physiological performance of phytoplankton. In order to learn how phytoplankton respond to the predicted scenario of increased CO2 and decreased nitrogen in the surface mixed layer, we investigated the diatom Phaeodactylum tricornutum as a model organism. The cells were cultured in both low CO2 (390 µatm) and high CO2 (1000 µatm) conditions at limiting (10 µmol/L) or enriched (110 µmol/L) nitrate concentrations. Our study shows that nitrogen limitation resulted in significant decreases in cell size, pigmentation, growth rate and effective quantum yield of Phaeodactylum tricornutum, but these parameters were not affected by enhanced dissolved CO2 and lowered pH. However, increased CO2 concentration induced higher rETRmax and higher dark respiration rates and decreased the CO2 or dissolved inorganic carbon (DIC) affinity for electron transfer (shown by higher values for K1/2 DIC or K1/2 CO2). Furthermore, the elemental stoichiometry (carbon to nitrogen ratio) was raised under high CO2 conditions in both nitrogen limited and nitrogen replete conditions, with the ratio in the high CO2 and low nitrate grown cells being higher by 45% compared to that in the low CO2 and nitrate replete grown ones. Our results suggest that while nitrogen limitation had a greater effect than ocean acidification, the combined effects of both factors could act synergistically to affect marine diatoms and related biogeochemical cycles in future oceans.

(Table S1) Globigerinoides sacculifer Boron isotope ratios of ODP Hole 165-999A

everal hypotheses have been put forward to explain the onset of intensive glaciations on Greenland, Scandinavia, and North America during the Pliocene epoch between 3.6 and 2.7 million years ago (Ma). A decrease in atmospheric CO2 may have played a role during the onset of glaciations, but other tectonic and oceanic events occurring at the same time may have played a part as well. Here we present detailed atmospheric CO2 estimates from boron isotopes in planktic foraminifer shells spanning 4.6-2.0 Ma. Maximal Pliocene atmospheric CO2 estimates gradually declined from values around 410 µatm to early Pleistocene values of 300 ?atm at 2.0 Ma. After the onset of large-scale ice sheets in the Northern Hemisphere, maximal pCO2 estimates were still at 2.5 Ma +90 µatm higher than values characteristic of the early Pleistocene interglacials. By contrast, Pliocene minimal atmospheric CO2 gradually decreased from 310 to 245 µatm at 3.2 Ma, coinciding with the start of transient glaciations on Greenland. Values characteristic of early Pleistocene glacial atmospheric CO2 of 200 ?atm were abruptly reached after 2.7 Ma during the late Pliocene transition. This trend is consistent with the suggestion that ocean stratification and iron fertilization increased after 2.7 Ma in the North Pacific and Southern Ocean and may have led to increased glacial CO2 storage in the oceanic abyss after 2.7 Ma onward.

Gas hydrate investigation at the Amsterdam mud volcano

We investigated gas hydrate in situ inventories as well as the composition and principal transport mechanisms of fluids expelled at the Amsterdam mud volcano (AMV; 2,025 m water depth) in the Eastern Mediterranean Sea. Pressure coring (the only technique preventing hydrates from decomposition during recovery) was used for the quantification of light hydrocarbons in near-surface deposits. The cores (up to 2.5 m in length) were retrieved with an autoclave piston corer, and served for analyses of gas quantities and compositions, and pore-water chemistry. For comparison, gravity cores from sites at the summit and beyond the AMV were analyzed. A prevalence of thermogenic light hydrocarbons was inferred from average C1/C2+ ratios <35 and d13C-CH4 values of -50.6 per mil. Gas venting from the seafloor indicated methane oversaturation, and volumetric gas-sediment ratios of up to 17.0 in pressure cores taken from the center demonstrated hydrate presence at the time of sampling. Relative enrichments in ethane, propane, and iso-butane in gas released from pressure cores, and from an intact hydrate piece compared to venting gas suggest incipient crystallization of hydrate structure II (sII). Nonetheless, the co-existence of sI hydrate can not be excluded from our dataset. Hydrates fill up to 16.7% of pore volume within the sediment interval between the base of the sulfate zone and the maximum sampling depth at the summit. The concave-down shapes of pore-water concentration profiles recorded in the center indicate the influence of upward-directed advection of low-salinity fluids/fluidized mud. Furthermore, the SO42- and Ba2+ pore-water profiles in the central part of the AMV demonstrate that sulfate reduction driven by the anaerobic oxidation of methane is complete at depths between 30 cm and 70 cm below seafloor. Our results indicate that methane oversaturation, high hydrostatic pressure, and elevated pore-water activity caused by low salinity promote fixing of considerable proportions of light hydrocarbons in shallow hydrates even at the summit of the AMV, and possibly also of other MVs in the region. Depending on their crystallographic structure, however, hydrates will already decompose and release hydrocarbon masses if sediment temperatures exceed ca. 19.3°C and 21.0°C, respectively. Based on observations from other mud volcanoes, the common occurrence of such temperatures induced by heat flux from below into the immediate subsurface appears likely for the AMV.

Seawater carbonate chemistry and biological processes of Emiliania huxleyi (strains RCC1256 and NZEH) during experiments, 2011

With respect to their sensitivity to ocean acidification, calcifiers such as the coccolithophore Emiliania huxleyi have received special attention, as the process of calcification seems to be particularly sensitive to changes in the marine carbonate system. For E. huxleyi, apparently conflicting results regarding its sensitivity to ocean acidification have been published (Iglesias-Rodriguez et al., 2008a; Riebesell et al., 2000). As possible causes for discrepancies, intra-specific variability and different effects of CO2 manipulation methods, i.e. the manipulation of total alkalinity (TA) or total dissolved inorganic carbon (DIC), have been discussed. While Langer et al. (2009) demonstrate a high degree of intra-specific variability between strains of E. huxleyi, the question whether different CO2 manipulation methods influence the cellular responses has not been resolved yet. In this study, closed TA as well as open and closed DIC manipulation methods were compared with respect to E. huxleyi's CO2-dependence in growth rate, POC- and PIC-production. The differences in the carbonate chemistry between TA and DIC manipulations were shown not to cause any differences in response patterns, while the latter differed between open and closed DIC manipulation. The two strains investigated showed different sensitivities to acidification of seawater, RCC1256 being more negatively affected in growth rates and PIC production than NZEH.

(Table 1) Radionuclides and ESR dating of sediment cores PS1535-10 and PS1535-8

ESR-spectra of foraminifera in arctic sediment cores display the [CO2]- -signal (g=2.0006). Research on the thermal behaviour of the [CO2]- -signal shows that both natural and artificial irradiation generates a precursor and a thermal unstable component of the [CO2]- -signal. The precursor can be transfered to the stable radical, and unstable radicals can be removed by heating. The signal-change by heating depends on the irradiation dose. Because of the varying response on thermal treatment, the dose-response curves show systematic differences depending on the applied procedure (single- or multi-aliquot method with or without heating). A model for the description of the [CO2]- -signal-change is presented. The combination of two exponential saturation functions seems to be an adequate analytical description of the dose-response curve of the [CO2]- -signal in foraminifera. Due to the limited thermal stability this signal can be used for dating foraminifera with ages up to about 190 ka.