Biogeochemical parameters (oxygen, nitrate, phosphate, TOC and strontium) at three sites from the Clarion-Clipperton Fracture Zone

The Clarion-Clipperton Fracture Zone (CCFZ) in the Pacific Ocean is characterized by organic carbon-starved sediments and meter-scale oxygen penetration into the sediment. Furthermore, numerous seamounts occur throughout its deep-sea plain, which may serve as conduits for low-temperature hydrothermal circulation of seawater through the oceanic crust. Recent studies in deep-sea environments of the Pacific and Atlantic Oceans have suggested and presented evidence of an exchange of dissolved constituents between the seawater flowing in the basaltic crust and the pore water of the overlying sediments. Through high-resolution pore-water oxygen and nutrient measurements, we examined fluxes and geochemical interactions between the seamount basaltic basement and pore waters of the overlying sediments at three sites located on a radial transect from the foot of Teddy Bare, a small seamount in the CCFZ. At three sites, located 1000, 700 and 400 m away from the foot of the seamount, we found that oxygen concentrations initially decrease with sediment depth but start to increase at depths of 3 and 7 m towards the basaltic basement. NO32- concentrations mirror the oxygen concentration profiles, as they increase with sediment depth but decrease towards the basement. We performed transport reaction modeling and determined at one site the 87Sr/86Sr ratio of the pore water and the bottom water overlying the sediments, which indicated that the 87Sr/86Sr ratio of the pore water at the bottom of the sediment column is similar to the seawater Transport-reaction modeling revealed that (1) the diffusive flux of oxygen from the basaltic basement outpaces the oxygen consumption through organic matter oxidation and nitrification in the basal sediments and (2) the nutrient exchange between the sediment and the underlying basaltic crust occurs at orders-of-magnitude lower rates than between the upper sediment and the overlying bottom water. Our results suggest an upward diffusion of oxygen from seawater circulating within the seamount crust into the overlying basal sediments. The oxygen profiles presented here represent the first of their kind ever measured in the Pacific Ocean, as they indicate an upward flux of molecular oxygen from a basaltic aquifer, something that has so far only been documented - at one other location worldwide - the North Pond site in the Atlantic Ocean. We show that the diffusion of oxygen from the seamount basaltic basement into the overlying pore waters affects the preservation of organic compounds and helps to maintain a completely oxygenated sedimentary column at all 3 sites near the seamount.

Interactions between water and triacylglycerols may explain faster aging rates in stored germplasm at low temperatures

The purpose of this research is to explore the extent and significance of possible interacting factors on the viability of stored germplasm. Our work begins with characterizing the kinetics of TAG and water phase changes in peanut (Arachis hypogaea) and Papaya (Carica papaya) seeds equilibrated to different water contents and stored at temperatures between -5 and -80°C. Water and TAG phase was measured using a Perkin Elmer Differential Scanning Calorimeter. Cytoplasm ultra-structure was visualized without chemical fixatives using low temperature scanning electron microscopy (cryo-SEM) performed with a Zeiss DSN 960 scanning microscope equipped with a Cryotrans CT-1500 cold plate (Oxford, UK).

On the electronic nature of low-barrier hydrogen bonds in enzymatic reactions

The electronic nature of low-barrier hydrogen bonds (LBHBs) in enzymatic reactions is discussed based on combined low temperature neutron and x-ray diffraction experiments and on high level ab initio calculations by using the model substrate benzoylacetone. This molecule has a LBHB, as the intramolecular hydrogen bond is described by a double-well potential with a small barrier for hydrogen transfer. From an “atoms in molecules” analysis of the electron density, it is found that the hydrogen atom is stabilized by covalent bonds to both oxygens. Large atomic partial charges on the hydrogen-bonded atoms are found experimentally and theoretically. Therefore, the hydrogen bond gains stabilization from both covalency and from the normal electrostatic interactions found for long, weak hydrogen bonds. Based on comparisons with other systems having short-strong hydrogen bonds or LBHBs, it is proposed that all short-strong and LBHB systems possess similar electronic features of the hydrogen-bonded region, namely polar covalent bonds between the hydrogen atom and both heteroatoms in question.

The influence of the flow of the reacting gas on the conditions for a thermal explosion

The classical problem of thermal explosion is modified so that the chemically active gas is not at rest but is flowing in a long cylindrical pipe. Up to a certain section the heat-conducting walls of the pipe are held at low temperature so that the reaction rate is small and there is no heat release; at that section the ambient temperature is increased and an exothermic reaction begins. The question is whether a slow reaction regime will be established or a thermal explosion will occur. The mathematical formulation of the problem is presented. It is shown that when the pipe radius is larger than a critical value, the solution of the new problem exists only up to a certain distance along the axis. The critical radius is determined by conditions in a problem with a uniform axial temperature. The loss of existence is interpreted as a thermal explosion; the critical distance is the safe reactor’s length. Both laminar and developed turbulent flow regimes are considered. In a computational experiment the loss of the existence appears as a divergence of a numerical procedure; numerical calculations reveal asymptotic scaling laws with simple powers for the critical distance.

Nitrate Transport and Not Photoinhibition Limits Growth of the Freshwater Cyanobacterium Synechococcus Species PCC 6301 at Low Temperature1

The effect of low temperature on cell growth, photosynthesis, photoinhibition, and nitrate assimilation was examined in the cyanobacterium Synechococcus sp. PCC 6301 to determine the factor that limits growth. Synechococcus sp. PCC 6301 grew exponentially between 20°C and 38°C, the growth rate decreased with decreasing temperature, and growth ceased at 15°C. The rate of photosynthetic oxygen evolution decreased more slowly with temperature than the growth rate, and more than 20% of the activity at 38°C remained at 15°C. Oxygen evolution was rapidly inactivated at high light intensity (3 mE m−2 s−1) at 15°C. Little or no loss of oxygen evolution was observed under the normal light intensity (250 μE m−2 s−1) for growth at 15°C. The decrease in the rate of nitrate consumption by cells as a function of temperature was similar to the decrease in the growth rate. Cells could not actively take up nitrate or nitrite at 15°C, although nitrate reductase and nitrite reductase were still active. These data demonstrate that growth at low temperature is not limited by a decrease in the rate of photosynthetic electron transport or by photoinhibition, but that inactivation of the nitrate/nitrite transporter limits growth at low temperature.

Interaction of Osmotic Stress, Temperature, and Abscisic Acid in the Regulation of Gene Expression in Arabidopsis

The impact of simultaneous environmental stresses on plants and how they respond to combined stresses compared with single stresses is largely unclear. By using a transgene (RD29A-LUC) consisting of the firefly luciferase coding sequence (LUC) driven by the stress-responsive RD29A promoter, we investigated the interactive effects of temperature, osmotic stress, and the phytohormone abscisic acid (ABA) in the regulation of gene expression in Arabidopsis seedlings. Results indicated that both positive and negative interactions exist among the studied stress factors in regulating gene expression. At a normal growth temperature (22°C), osmotic stress and ABA act synergistically to induce the transgene expression. Low temperature inhibits the response to osmotic stress or to combined treatment of osmotic stress and ABA, whereas low temperature and ABA treatments are additive in inducing transgene expression. Although high temperature alone does not activate the transgene, it significantly amplifies the effects of ABA and osmotic stress. The effect of multiple stresses in the regulation of RD29A-LUC expression in signal transduction mutants was also studied. The results are discussed in the context of cold and osmotic stress signal transduction pathways.

Expression of Small Heat-Shock Proteins at Low Temperatures1 : A Possible Role in Protecting against Chilling Injuries

We previously reported that short exposure of tomato (Lycopersicon esculentum L.) fruits to high temperature protects them from chilling injury. To study the involvement of heat-shock proteins (HSPs) in the acquisition of low-temperature tolerance, we cloned two heat-shock-induced genes that are also expressed at low temperatures. The cloned cDNAs belong to the small HSP group. Sequence analyses of the clones showed perfect homology to the tomato-ripening gene tom66 and to the tomato chloroplastic HSP21 gene tom111. The expression of both genes was induced by high temperature in fruits, flowers, leaves, and stems, but not by low or ambient temperatures or by other stresses such as drought and anaerobic conditions. When the heated fruits were transferred to low temperature, tom66 and tom111 mRNA levels first decreased but were then reinduced. Induction was not observed in nonheated fruits at low temperature. Immunodetection of tom111-encoded protein indicated that this protein is present at low temperatures in the heated fruits. The results of this study show that the expression of tom66 and tom111 is correlated with protection against some, but not all, symptoms of chilling injury.

Bathorhodopsin structure in the room-temperature rhodopsin photosequence: picosecond time-resolved coherent anti-Stokes Raman scattering.

Structural changes in the retinal chromophore during the formation of the bathorhodopsin intermediate (bathoRT) in the room-temperature rhodopsin (RhRT) photosequence (i.e., vision) are examined using picosecond time-resolved coherent anti-Stokes Raman scattering. Specifically, the retinal structure assignable to bathoRT following 8-ps excitation of RhRT is measured via vibrational Raman spectroscopy at a 200-ps time delay where the only intermediate present is bathoRT. Significant differences are observed between the C=C stretching frequencies of the retinal chromophore at low temperature where bathorhodopsin is stabilized and at room temperature where bathorhodopsin is a transient species in the RhRT photosequence. These vibrational data are discussed in terms of the formation of bathoRT, an important step in the energy storage/transduction mechanism of RhRT.

A gene encoding a phosphatidylinositol-specific phospholipase C is induced by dehydration and salt stress in Arabidopsis thaliana.

A cDNA corresponding to a putative phosphatidylinositol-specific phospholipase C (PI-PLC) in the higher plant Arabidopsis thaliana was cloned by use of the polymerase chain reaction. The cDNA, designated cAtPLC1, encodes a putative polypeptide of 561 aa with a calculated molecular mass of 64 kDa. The putative product includes so-called X and Y domains found in all PI-PLCs identified to date. In mammalian cells, there are three types of PI-PLC, PLC-beta, -gamma, and -delta. The overall structure of the putative AtPLC1 protein is most similar to that of PLC-delta, although the AtPLC1 protein is much smaller than PLCs from other organisms. The recombinant AtPLC1 protein synthesized in Escherichia coli was able to hydrolyze phosphatidylinositol 4,5-bisphosphate and this activity was completely dependent on Ca2+, as observed also for mammalian PI-PLCs. These results suggest that the AtPLC1 gene encodes a genuine PI-PLC of a higher plant. Northern blot analysis showed that the AtPLC1 gene is expressed at very low levels in the plant under normal conditions but is induced to a significant extent under various environmental stresses, such as dehydration, salinity, and low temperature. These observations suggest that AtPLC1 might be involved in the signal-transduction pathways of environmental stresses and that an increase in the level of AtPLC1 might amplify the signal, in a manner that contributes to the adaptation of the plant to these stresses.

Photocatalytic oxidation of propene in gas phase at low concentration by optimized TiO2 nanoparticles

In the present study, nanocrystalline titanium dioxide (TiO2) was prepared by sol–gel method at low temperature from titanium tetraisopropoxide (TTIP) and characterized by different techniques (gas adsorption, XRD, TEM and FTIR). Variables of the synthesis, such as the hydrolyzing agent (acetic acid or isopropanol) and calcination temperatures (300–800 °C), were analyzed to get uniform size TiO2 nanoparticles. The effect that these two variables have on the structure of the resultant TiO2 nanoparticles and on their photocatalytic activity is investigated. The photocatalytic activities of TiO2 nanoparticles were evaluated for propene oxidation at low concentration (100 ppmv) under two different kinds of UV light (UV-A ∼ 365 nm and UV-C ∼ 257.7 nm) and compared with Degussa TiO2 P-25, used as reference sample. The results show that both hydrolyzing agents allow to prepare TiO2 nanoparticles and that the hydrolyzing agent influences the crystalline structure and its change with the thermal treatments. Interestingly, the prepared TiO2 nanoparticles possess anatase phase with small crystalline size, high surface area and higher photocatalytic activity for propene oxidation than commercial TiO2 (Degussa P-25) under UV-light. Curiously, these prepared TiO2 nanoparticles are more active with the 365 nm source than with the 257.7 nm UV-light, which is a remarkable advantage from an application point of view. Additionally, the obtained results are particularly good when acetic acid is the hydrolyzing agent at both wavelengths used, possibly due to the high crystallinity, low anatase phase size and high surface oxygen groups’ content in the nanoparticles prepared with it, in comparison to those prepared using isopropanol.

Stable isotope ratios of interstitial fluids from ODP Leg 110 sites

Delta18O values of pore waters from the northern Barbados accretionary prism range from -0.3 to -3.6? and reflect pervasive reaction of volcanic ash to form smectite within the sedimentary sequence and continued low temperature alteration of basalt in the underlying ocean crust with the overprint of diffusive exchange between water in the sediment pores and the open ocean. Delta D values of pore waters in sediments sampled seaward of the deformation front drop from +5? at the sediment surface to -6? at the deepest levels sampled. These changes may also be related to alteration processes but remain largely enigmatic. Sediment deformation caused by impingement of the Caribbean plate on the Atlantic plate has instigated migration of chemically and isotopically distinct fluid along faults and coarse-grained sedimentary beds; delta18O values of pore waters are also locally affected by thrust stacking which increases diffusive pathlengths and possibly modifies diagenetic reaction rates in Pleistocene sediments. Migrating fluids are distinguished by anomalous delta18O values that are as much as 1? higher than those of surrounding fluids. Uncertainties in hydrogen isotope fractionation resulting from processes occurring under these conditions hinder identification of the hydrogen isotope composition of expelled fluid. Stable isotope analyses of pore waters help constrain the fluid migration history of the accretionary prism by limiting the source of fluids, the paths along which fluid flows, and the timing of faulting and subsequent fluid flow.

Sulfur isotope rations in oceanic basement samples

Low temperature alteration of oceanic basement rocks is characterized by net gain of sulfur, which commonly yields low d34S values, suggesting involvement of microbial sulfate reduction. In order to test whether secondary sulfide minerals are consistent with a biogenic source, we apply high precision multiple sulfur isotope analysis to bulk rock sulfide and pyrite isolates from two contrasting types of altered oceanic basement rocks, namely serpentinized peridotites and altered basalts. Samples from two peridotite sites (Iberian Margin and Hess Deep) and from a basalt site on the eastern flank of the Juan de Fuca Ridge yield overlapping d34S values ranging from 0 per mil to -44 per mil. In contrast, sulfides in the basalt site are characterized by relatively low D33S values ranging from -0.06 per mil to 0.04 per mil, compared to those from peridotite sites (0.00 per mil to 0.16 per mil). The observed D33S signal is significant considering the analytical precision of 0.014 per mil (2 sigma). We present a batch reaction model that uses observed d34S and D33S relationships to quantify the effect of closed system processes and constrain the isotope enrichment factor intrinsic to sulfate reduction. The estimated enrichment factors as large as 61 per mil and 53 per mil, for peridotite and basalt sites respectively, suggest the involvement of microbial sulfate reduction. The relatively high D33S values in the peridotite sites are due to sulfate reduction in a closed system environment, whereas negative D33S values in the basalt site reflect open system sulfate reduction. A larger extent of sulfate reduction during alteration of peridotite to serpentinite is consistent with its higher H2 production capacity compared to basalt alteration, and further supports in-situ microbial sulfate reduction coupled with H2 production during serpentinization reactions.

In situ measurements of hydrogen sulfide, oxygen, and temperature in diffuse fluids of the ultramafic-hosted Logatchev hydrothermal vent field (Mid-Atlantic Ridge)

The Logatchev hydrothermal vent field (14°45'N, Mid-Atlantic Ridge) is located in a ridge segment characterized by mantle-derived ultramafic outcrops. Compared to basalt-hosted vents, Logatchev high temperature fluids are relatively low in sulfide indicating that the diffuse, low temperature fluids of this vent field may not contain sufficient sulfide concentrations to support a chemosymbiotic invertebrate community. However, the high abundances of bathymodiolin mussels with bacterial symbionts related to free-living sulfur oxidizing bacteria suggested that bioavailable sulfide is present at Logatchev. To clarify if diffuse fluids above mussel beds of Bathymodiolus puteoserpentis provide the reductants and oxidants needed by their symbionts for aerobic sulfide oxidation, in situ microsensor measurements of dissolved hydrogen sulfide and oxygen were combined with simultaneous temperature measurements. High temporal fluctuations of all three parameters were measured above the mussel beds. H2S and O2 co-existed with mean concentrations between 9-31 µM (H2S) and 216-228 µM (O2). Temperature maxima (<= 7.4°C) were generally concurrent with H2S maxima (<= 156 µM) and O2 minima (>= 142 µM). Long-term measurements for 250 days using temperature as a proxy for oxygen and sulfide concentrations indicated that the mussels were neither oxygen- nor sulfide-limited. Our in situ measurements at Logatchev indicate that sulfide may also be bioavailable in diffuse fluids from other ultramafic-hosted vents along slow- and ultraslow-spreading ridges.

(Table 2) Geochemistry at DSDP Holes 62-464 and 62-465A

Igneous rocks were recovered from three sites on Hess Rise during Deep Sea Drilling Project Leg 62: altered basalt at Site 464, at the northern end of Hess Rise; and altered trachyte from Site 465, and rounded basalt pebbles in upper Albian to middle Miocene sediments from Site 466, both at the southern end of Hess Rise. Major-, minor-, and trace-element data for basalt from Hole 464 are consistent with these rocks being transitional tholeiites that have undergone low-temperature alteration by reaction with sea water. Trachyte from Hole 465A exhibits as many as three generations of plagioclase along with potash feldspar that are flow aligned in groundmasses alterted to smectites and random mixed-layer clays. Textural evidence indicates that these rocks were eruped subaerially. Chemical data show a range of values when plotted on two- and three-component variation diagrams. The observed variations may result in part from differentiation, but they also reflect the high degree of alteration. Several oxides and elements show strong correlation with H2O+: K2O, SiO2, Rb and Lu decrease and MgO increases with increasing H2O+. These trends, except for that of Lu, are consistent with experimentally determined changes in chemistry that accompany alteration. The trend for Lu has not been previously reported; it may result from a more-intense alteration of the HREE-rich mafic minerals than of the LREE-rich feldspars. Despite their alteration, the trachytes compare favorably with alkalic differentiates from oceanic islands. We interpret Hess Rise as a volcanic platform formed by eruption of off-ridge volcanic rocks onto MORB oceanic crust during the Aptian and Albian stages, after the basement had migrated away from the spreading center. By analogy with present oceanic islands, we propose that early tholeiitic basalts were followed by alkalic basalts and their differentiation products (trachytes), producing a volcanic archipelago of islands and seamounts. Subsequent tectonism and subsidence led to the present state of Hess Rise.

Rb-Sr systematics of volcanic rocks and alteration minerals of ODP Hole 104-642E

Subaerially erupted tholeiites at Hole 642E were never exposed to the high-temperature seawater circulation and alteration conditions that are found at subaqueous ridges. Alteration of Site 642 rocks is therefore the product of the interaction of rocks and fluids at low temperatures. The alteration mineralogy can thus be used to provide information on the geochemical effects of low temperature circulation of seawater. Rubidium-strontium systematics of leached and unleached tholeiites and underlying, continentally-derived dacites reflect interactions with seawater in fractures and vesicular flow tops. The secondary mineral assemblage in the tholeiites consists mainly of smectite, accompanied in a few flows by the assemblage celadonite + calcite (+/- native Cu). Textural relationships suggest that smectites formed early and that celadonite + calcite, which are at least in part cogenetic, formed later than and partially at the expense of smectite. Smectite precipitation occurred under variable, but generally low, water/rock conditions. The smectites contain much lower concentrations of alkali elements than has been reported in seafloor basalts, and sequentially leached fractions of smectite contain Sr that has not achieved isotopic equilibrium. 87Sr/86Sr results of the leaching experiments suggest that Sr was mostly derived from seawater during early periods of smectite precipitation. The basalt-like 87Sr/86Sr of the most readily exchangeable fraction seems to suggest a late period of exposure to very low water /rock. Smectite formation may have primarily occurred in the interval between the nearly 58-Ma age given by the lower series dacites and the 54.5 +/- 0.2 Ma model age given by a celadonite from the top of the tholeiitic section. The 54.5 +/- 0.2 Ma Rb-Sr model age may be recording the timing of foundering of the Voring Plateau. Celadonites precipitated in flows below the top of the tholeiitic section define a Rb-Sr isochron with a slope corresponding to an age of 24.3 +/- 0.4 Ma. This isochron may be reflecting mixing effects due to long-term chemical interaction between seawater and basalts, in which case the age provides only a minimum for the timing of late alteration. Alternatively, inferrential arguments can be made that the 24.3 +/- 0.4 isochron age reflects the timing of the late Oligocene-early Miocene erosional event that affected the Norwegian-Greenland Sea. Correlation of 87Sr/86Sr and 1/Sr in calcites results in a two-component mixing model for late alteration products. One end-member of the mixing trend is Eocene or younger seawater. Strontium from the nonradiogenic endmember can not, however, have been derived directly from the basalts. Rather, the data suggest that Sr in the calcites is a mixture of Sr derived from seawater and from pre-existing smectites. For Site 642, the reaction involved can be generalized as smectite + seawater ++ celadonite + calcite. The geochemical effects of this reaction include net gains of K and CO2 by the secondary mineral assemblage. The gross similarity of the reactions involved in late, low-temperature alteration at Site 642 to those observed in other sea floor basalts suggests that the transfer of K and C02 to the crust during low-temperature seawater-ocean crust interactions may be significant in calculations of global fluxes.