Reactive mass transport modelling of a three-dimensional vertical fault zone with a finger-like convective flow regime

For a three-dimensional vertically-oriented fault zone, we consider the coupled effects of fluid flow, heat transfer and reactive mass transport, to investigate the patterns of fluid flow, temperature distribution, mineral alteration and chemically induced porosity changes. We show, analytically and numerically, that finger-like convection patterns can arise in a vertically-oriented fault zone. The onset and patterns of convective fluid flow are controlled by the Rayleigh number which is a function of the thermal properties of the fluid and the rock, the vertical temperature gradient, and the height and the permeability of the fault zone. Vigorous fluid flow causes low temperature gradients over a large region of the fault zone. In such a case, flow across lithological interfaces becomes the most important mechanism for the formation of sharp chemical reaction fronts. The degree of rock buffering, the extent and intensity of alteration, the alteration mineralogy and in some cases the formation of ore deposits are controlled by the magnitude of the flow velocity across these compositional interfaces in the rock. This indicates that alteration patterns along compositional boundaries in the rock may provide some insights into the convection pattern. The advective mass and heat exchanges between the fault zone and the wallrock depend on the permeability contrast between the fault zone and the wallrock. A high permeability contrast promotes focussed convective flow within the fault zone and diffusive exchange of heat and chemical reactants between the fault zone and the wallrock. However, a more gradual permeability change may lead to a regional-scale convective flow system where the flow pattern in the fault affects large-scale fluid flow, mass transport and chemical alteration in the wallrocks

Conformational diversity versus nucleic acid triplex stability, a combinatorial study

The stability of a triple helix formed between a DNA duplex and an incoming oligonucleotide strand strongly depends on the solvent conditions and on intrinsic chemical and conformational factors. Attempts to increase triple helix stability in the past included chemical modification of the backbone, sugar ring, and bases in the third strand. However, the predictive power of such modifications is still rather poor. We therefore developed a method that allows for rapid screening of conformationally diverse third strand oligonucleotides for triplex stability in the parallel pairing motif to a given DNA double helix sequence. Combinatorial libraries of oligonucleotides of the requisite (fixed) base composition and length that vary in their sugar unit (ribose or deoxyribose) at each position were generated. After affinity chromatography against their corresponding immobilized DNA target duplex, utilizing a temperature gradient as the selection criterion, the oligonucleotides forming the most stable triple helices were selected and characterized by physicochemical methods. Thus, a series of oligonucleotides were identified that allowed us to define basic rules for triple helix stability in this conformationally diverse system. It was found that ribocytidines in the third strand increase triplex stability relative to deoxyribocytidines independently of the neighboring bases and position along the strand. However, remarkable sequence-dependent differences in stability were found for (deoxy)thymidines and uridines

Interaction of corroding iron with bentonite in the ABM1 experiment at Äspö, Sweden: A microscopic approach

Bentonite and iron metals are common materials proposed for use in deep-seated geological repositories for radioactive waste. The inevitable corrosion of iron leads to interaction processes with the clay which may affect the sealing properties of the bentonite backfill. The objective of the present study was to improve our understanding of this process by studying the interface between iron and compacted bentonite in a geological repository-type setting. Samples of MX-80 bentonite samples which had been exposed to an iron source and elevated temperatures (up to 115ºC) for 2.5 y in an in situ experiment (termed ABM1) at the Äspö Hard Rock Laboratory, Sweden, were investigated by microscopic means, including scanning electron microscopy, μ-Raman spectroscopy, spatially resolved X-ray diffraction, and X-ray fluorescence. The corrosion process led to the formation of a ~100 mm thick corrosion layer containing siderite, magnetite, some goethite, and lepidocrocite mixed with the montmorillonitic clay. Most of the corroded Fe occurred within a 10 mm-thick clay layer adjacent to the corrosion layer. An average corrosion depth of the steel of 22–35 μm and an average Fe2+ diffusivity of 1–26×10–13 m2/s were estimated based on the properties of the Fe-enriched clay layer. In that layer, the corrosion-derived Fe occurred predominantly in the clay matrix. The nature of this Fe could not be identified. No indications of clay transformation or newly formed clay phases were found. A slight enrichment of Mg close to the Fe–clay contact was observed. The formation of anhydrite and gypsum, and the dissolution of some SiO2 resulting from the temperature gradient in the in situ test, were also identified. © 2014, Clay Minerals Society. All right reserved.

Reduction of cement leakage by sequential PMMA application in a vertebroplasty model

PURPOSE Leakage is the most common complication of percutaneous cement augmentation of the spine. The viscosity of the polymethylmethacrylate (PMMA) cement is strongly correlated with the likelihood of cement leakage. We hypothesized that cement leakage can be reduced by sequential cement injection in a vertebroplasty model. METHODS A standardized vertebral body substitute model, consisting of aluminum oxide foams coated by acrylic cement with a preformed leakage path, simulating a ventral vein, was developed. Three injection techniques of 6 ml PMMA were assessed: injection in one single step (all-in-one), injection of 1 ml at the first and 5 ml at the second step with 1 min latency in-between (two-step), and sequential injection of 0.5 ml with 1-min latency between the sequences (sequential). Standard PMMA vertebroplasty cement was used; each injection type was tested on ten vertebral body substitute models with two possible leakage paths per model. Leakage was assessed by radiographs using a zonal graduation: intraspongious = no leakage and extracortical = leakage. RESULTS The leakage rate was significantly lower in the "sequential" technique (2/20 leakages) followed by "two-step" (15/20) and "all-in-one" (20/20) techniques (p < 0.001). The RR for a cement leakage was 10.0 times higher in the "all-in-one" compared to the "sequential" group (95 % confidence intervals 2.7-37.2; p < 0.001). CONCLUSIONS The sequential cement injection is a simple approach to minimize the risk for leakage. Taking advantage of the temperature gradient between body and room temperature, it is possible to increase the cement viscosity inside the vertebra while keeping it low in the syringe. Using sequential injection of small cement volumes, further leakage paths are blocked before further injection of the low-viscosity cement.

Circulating oxidized low-density lipoprotein (LDL) is associated with risk factors of the metabolic syndrome and LDL size in clinically healthy 58-year-old men (AIR study).

OBJECTIVES Hypothetically the atherogenic effect of the metabolic syndrome may be mediated through the increased occurrence of small LDL-particles which are easily modified to atherogenic oxidized LDL (ox-LDL). The aim of this study was to test this concept by examining the association between circulating ox-LDL, LDL-particle size, and the metabolic syndrome. DESIGN AND RESULTS A population-based sample of clinically healthy 58-year-old men (n = 391) was recruited. Ox-LDL was measured by ELISA (specific monoclonal antibody, mAb-4E6) and LDL-particle size by gradient gel electrophoresis. The results showed that ox-LDL significantly correlated to factors constituting the metabolic syndrome; triglycerides (r = 0.43), plasma insulin (r = 0.20), body mass index (r = 0.20), waist-to-hip ratio (r = 0.21) and HDL (r = -0.24); (P < 0.001). Ox-LDL correlated also to LDL-particle size (r = -0.42), Apo-B (r = 0.70), LDL (r = 0.65); (P < 0.001) and, furthermore, with Apo A-1 (r = -0.13) and heart rate (r = 0.13); (P < 0.01). CONCLUSION The metabolic syndrome was accompanied by high plasma ox-LDL concentrations compared with those without the syndrome. Ox-LDL levels were associated with most of the risk factors constituting the metabolic syndrome and was, in addition related to small LDL-particle size. To our knowledge the present study is the first one to demonstrate that circulating ox-LDL levels are associated with small LDL-particle size in a population representative sample of clinically healthy middle-aged men. The high degree of intercorrelation amongst several factors makes it difficult to clarify the independent role of any specific factor.

Variability of daily winter wind speed distribution over Northern Europe during the past millennium in regional and global climate simulations

We analyse the variability of the probability distribution of daily wind speed in wintertime over Northern and Central Europe in a series of global and regional climate simulations covering the last centuries, and in reanalysis products covering approximately the last 60 years. The focus of the study lies on identifying the link of the variations in the wind speed distribution to the regional near-surface temperature, to the meridional temperature gradient and to the North Atlantic Oscillation. Our main result is that the link between the daily wind distribution and the regional climate drivers is strongly model dependent. The global models tend to behave similarly, although they show some discrepancies. The two regional models also tend to behave similarly to each other, but surprisingly the results derived from each regional model strongly deviates from the results derived from its driving global model. In addition, considering multi-centennial timescales, we find in two global simulations a long-term tendency for the probability distribution of daily wind speed to widen through the last centuries. The cause for this widening is likely the effect of the deforestation prescribed in these simulations. We conclude that no clear systematic relationship between the mean temperature, the temperature gradient and/or the North Atlantic Oscillation, with the daily wind speed statistics can be inferred from these simulations. The understand- ing of past and future changes in the distribution of wind speeds, and thus of wind speed extremes, will require a detailed analysis of the representation of the interaction between large-scale and small-scale dynamics.

Development of combined micro -preparation, separation, and mass spectrometry methods and application in the microdialysis study of neuropeptide metabolism

Two sets of mass spectrometry-based methods were developed specifically for the in vivo study of extracellular neuropeptide biochemistry. First, an integrated micro-concentration/desalting/matrix-addition device was constructed for matrix-assisted laser desorption ionization mass spectrometry (MALDI MS) to achieve attomole sensitivity for microdialysis samples. Second, capillary electrophoresis (CE) was incorporated into the above micro-liquid chromatography (LC) and MALDI MS system to provide two-dimensional separation and identification (i.e. electrophoretic mobility and molecular mass) for the analysis of complex mixtures. The latter technique includes two parts of instrumentation: (1) the coupling of a preconcentration LC column to the inlet of a CE capillary, and (2) the utilization of a matrix-precoated membrane target for continuous CE effluent deposition and for automatic MALDI MS analysis (imaging) of the CE track.^ Initial in vivo data reveals a carboxypeptidase A (CPA) activity in rat brain involved in extracellular neurotensin metabolism. Benzylsuccinic acid, a CPA inhibitor, inhibited neurotensin metabolite NT1-12 formation by 70%, while inhibitors of other major extracellular peptide metabolizing enzymes increased NT1-12 formation. CPA activity has not been observed in previous in vitro experiments. Next, the validity of the methodology was demonstrated in the detection and structural elucidation of an endogenous neuropeptide, (L)VV-hemorphin-7, in rat brain upon ATP stimulation. Finally, the combined micro-LC/CE/MALDI MS was used in the in vivo metabolic study of peptide E, a mu-selective opioid peptide with 25 amino acid residues. Profiles of 88 metabolites were obtained, their identity being determined by their mass-to-charge ratio and electrophoretic mobility. The results indicate that there are several primary cleavage sites in vivo for peptide E in the release of its enkephalin-containing fragments. ^

Great Barrier Reef coral element/Ca and stable isotope data and U-Th ages from IODP Expedition 325

Tropical south-western Pacific temperatures are of vital importance to the Great Barrier Reef (GBR), but the role of sea surface temperatures (SSTs) in the growth of the GBR since the Last Glacial Maximum remains largely unknown. Here we present records of Sr/Ca and d18O for Last Glacial Maximum and deglacial corals that show a considerably steeper meridional SST gradient than the present day in the central GBR. We find a 1-2 °C larger temperature decrease between 17° and 20°S about 20,000 to 13,000 years ago. The result is best explained by the northward expansion of cooler subtropical waters due to a weakening of the South Pacific gyre and East Australian Current. Our findings indicate that the GBR experienced substantial meridional temperature change during the last deglaciation, and serve to explain anomalous deglacial drying of northeastern Australia. Overall, the GBR developed through significant SST change and may be more resilient than previously thought.

Foraminifer counts in core JM01-1199, and review of radiocarbon ages in the Norwegian-Barents Sea-Svalbard margin

We compare six high-resolution Holocene, sediment cores along a S-N transect on the Norwegian-Svalbard continental margin from ca 60°N to 77.4°N, northern North Atlantic. Planktonic foraminifera in the cores were investigated to show the changes in upper surface and subsurface water mass distribution and properties, including summer sea-surface temperatures (SST). The cores are located below the axis of the Norwegian Current and the West Spitsbergen Current, which today transport warm Atlantic Water to the Arctic. Sediment accumulation rates are generally high at all the core sites, allowing for a temporal resolution of 10-102 years. SST is reconstructed using different types of transfer functions, resulting in very similar SST trends, with deviations of no more than +- 1.0/1.5 °C. A transfer function based on the maximum likelihood statistical approach is found to be most relevant. The reconstruction documents an abrupt change in planktonic foraminiferal faunal composition and an associated warming at the Younger Dryas-Preboreal transition. The earliest part of the Holocene was characterized by large temperature variability, including the Preboreal Oscillations and the 8.2 k event. In general, the early Holocene was characterized by SSTs similar to those of today in the south and warmer than today in the north, and a smaller S-N temperature gradient (0.23 °C/°N) compared to the present temperature gradient (0.46 °C/°N). The southern proxy records (60-69°N) were more strongly influenced by slightly cooler subsurface water probably due to the seasonality of the orbital forcing and increased stratification due to freshening. The northern records (72-77.4°N) display a millennial-scale change associated with reduced insolation and a gradual weakening of the North Atlantic thermohaline circulation (THC). The observed northwards amplification of the early Holocene warming is comparable to the pattern of recent global warming and future climate modelling, which predicts greater warming at higher latitudes. The overall trend during mid and late Holocene was a cooling in the north, stable or weak warming in the south, and a maximum S-N SST gradient of ca 0.7 °C/°N at 5000 cal. years BP. Superimposed on this trend were several abrupt temperature shifts. Four of these shifts, dated to 9000-8000, 5500-3000 and 1000 and ~400 cal. years BP, appear to be global, as they correlate with periods of global climate change. In general, there is a good correlation between the northern North Atlantic temperature records and climate records from Norway and Svalbard.

Geophysical logging on sediment core and hole CRP-3 from the Ross Sea, Antarctica

Cape Roberts drillhole CRP-3 in the northern part of McMurdo Sound (Ross Sea, Antarctica) targeted the western margin of the Victoria Land basin to investigate Neogene to Palaeogene climatic and tectonic history by obtaining continuous core and downhole logs (Cape Roberts Science Team, 2000). The CRP-3 drillhole extended to 939.42 mbsf (meters below seafloor) at a water depth of 297 m. The first downhole measurements after drilling were the temperature and salinity logs. Both were measured at the beginning and at the end of each of the three logging phases. Although an equilibrium temperature state may not have been fully reached after drilling, the temperature and salinity profiles seem to be scarcely disturbed. The average overall temperature gradient calculated from all temperature measurements is 28.5 K/km; remarkably lower than the temperature gradients found in other boreholes in the western Ross See and the Transantarctic Mountains. Anomalies in the salinity profiles at the beginning of each logging phase were no longer present at the end of the corresponding logging phase. This pattern indicates that drilling mud invaded the formation during drilling operations and flowed back into the borehole after drilling ceased. Thus, zones of temperature and salinity anomalies identify permeable zones in the formation and may be pathways for fluid flow. Radiogenic heat production, calculated from the radionuclide contents, is relatively low, with average values between 0.5 and 1.0 pW/m3. The highest values (up to 2 µW/m3) were obtained for the lower part of the Beacon Sandstone below 855 mbsf. The heat flow component due to radiogenic heat production integrated over the entire borehole is 0.7 mW/m2. Thermal conductivities range from 1.3 to 3 W/mK with an average value of 2.1 W/mK over the Tertiary section. Together with the average temperature gradient of 28.5 K/km this yields an average heat flow value of 60 mW/m2.

Compound specific stable isotopes, BIT, pollen and spores of Miocene to Pliocene sediments of ODP Hole 175-1085A

Pollen and stable carbon (d13C) and hydrogen (dD) isotope ratios of terrestrial plant wax from the South Atlantic sediment core, ODP Site 1085, is used to reconstruct Miocene to Pliocene changes of vegetation and rainfall regime of western southern Africa. Our results reveal changes in the relative amount of precipitation and indicate a shift of the main moisture source from the Atlantic to the Indian Ocean during the onset of a major aridification 8 Ma ago. We emphasise the importance of declining precipitation during the expansion of C4 and CAM (mainly succulent) vegetation in South Africa. We suggest that the C4 plant expansion resulted from an increased equator-pole temperature gradient caused by the initiation of strong Atlantic Meridional Overturning Circulation following the shoaling of the Central American Seaway during the Late Miocene.

Ice and snow measurements during Nathaniel B. Palmer cruise NBP0709 (SIMBA experiment)

The Sea Ice Mass Balance in the Antarctic (SIMBA) experiment was conducted from the RVIB N.B. Palmer in September and October 2007 in the Bellingshausen Sea in an area recently experiencing considerable changes in both climate and sea ice cover. Snow and ice properties were observed at 3 short-term stations and a 27-day drift station (Ice Station Belgica, ISB) during the winter-spring transition. Repeat measurements were performed on sea ice and snow cover at 5 ISB sites, each having different physical characteristics, with mean ice (snow) thicknesses varying from 0.6 m (0.1 m) to 2.3 m (0.7 m). Ice cores retrieved every five days from 2 sites and measured for physical, biological, and chemical properties. Three ice mass-balance buoys (IMBs) provided continuous records of snow and ice thickness and temperature. Meteorological conditions changed from warm fronts with high winds and precipitation followed by cold and calm periods through four cycles during ISB. The snow cover regulated temperature flux and controlled the physical regime in which sea ice morphology changed. Level thin ice areas had little snow accumulation and experienced greater thermal fluctuations resulting in brine salinity and volume changes, and winter maximum thermodynamic growth of ~0.6 m in this region. Flooding and snow-ice formation occurred during cold spells in ice and snow of intermediate thickness. In contrast, little snow-ice formed in flooded areas with thicker ice and snow cover, instead nearly isothermal, highly permeable ice persisted. In spring, short-lived cold air episodes did not effectively penetrate the sea ice nor overcome the effect of ocean heat flux, thus favoring net ice thinning from bottom melt over ice thickening from snow-ice growth, in all cases. These warm ice conditions were consistent with regional remote sensing observations of earlier ice breakup and a shorter sea ice season, more recently observed in the Bellingshausen Sea.

Climate and soil characteristics and soil arthropod abundance on Anchorage, Signy and Falkland Islands

Over a 2-year study, we investigated the effect of environmental change on the diversity and abundance of soil arthropod communities (Acari and Collembola) in the Maritime Antarctic and the Falkland Islands. Open Top Chambers (OTCs), as used extensively in the framework of the northern boreal International Tundra Experiment (ITEX), were used to increase the temperature in contrasting communities on three islands along a latitudinal temperature gradient, ranging from the Falkland Islands (51°S, mean annual temperature 7.5 °C) to Signy Island (60°S, -2.3°C) and Anchorage Island (67°S, -3.8°C). At each island an open and a closed plant community were studied: lichen vs. moss at the Antarctic sites, and grass vs. dwarf shrub at the Falkland Islands. The OTCs raised the soil surface temperature during most months of the year. During the summer the level of warming achieved was 1.7 °C at the Falkland Islands, 0.7 °C at Signy Island, and 1.1 °C at Anchorage Island. The native arthropod community diversity decreased with increasing latitude. In contrast with this pattern, Collembola abundance in the closed vegetation (dwarf shrub or moss) communities increased by at least an order of magnitude from the Falkland Islands (9.0 +/- 2 x 10**3 ind./m**2) to Signy (3.3 +/- 8.0 x 10**4 ind./m**2) and Anchorage Island (3.1 +/- 0.82 x 10**5 ind./m**2). The abundance of Acari did not show a latitudinal trend. Abundance and diversity of Acari and Collembola were unaffected by the warming treatment on the Falkland Islands and Anchorage Island. However, after two seasons of experimental warming, the total abundance of Collembola decreased (p < 0.05) in the lichen community on Signy Island as a result of the population decline of the isotomid Cryptopygus antarcticus. In the same lichen community there was also a decline (p < 0.05) of the mesostigmatid predatory mite Gamasellus racovitzai, and a significant increase in the total number of Prostigmata. Overall, our data suggest that the consequences of an experimental temperature increase of 1-2°C, comparable to the magnitude currently seen through recent climate change in the Antarctic Peninsula region, on soil arthropod communities in this region may not be similar for each location but is most likely to be small and initially slow to develop.