Effect of tin-chloride pretreatment on bond strength of two adhesive systems to dentin

OBJECTIVES: To determine the effect on resin composite-to-dentin bond strength of incorporation of an acidic tin-chloride pretreatment in two adhesive systems. MATERIALS AND METHODS: Human molars were ground to expose mid-coronal dentin. For microtensile bond strength (μTBS) testing, dentin was treated with Optibond FL or Clearfil SE according to one of six protocols (n = 22/group). Group 1: Phosphoric acid etching, Optibond FL Prime, Optibond FL Adhesive (manufacturer's instructions; control); Group 2: Tin-chloride pretreatment, Optibond FL Prime, Optibond FL Adhesive; Group 3: Phosphoric acid etching, tin-chloride pretreatment, Optibond FL Prime, Optibond FL Adhesive; Group 4: Clearfil SE Primer, Clearfil SE Bond (manufacturer's instructions; control); Group 5: Phosphoric acid etching, Clearfil SE Primer, Clearfil SE Bond; and Group 6: Tin-chloride pretreatment, Clearfil SE Primer, Clearfil SE Bond. The molars were then built up with resin composite (Clearfil Majesty Esthetic). After storage (1 week, 100  % humidity, 37 °C) the μTBS was measured and failure mode was determined. Additionally, pretreated dentin surfaces were evaluated using SEM and EDX. The μTBS results were analyzed statistically by a Welch Two Sample t-test and a Kruskal-Wallis test followed by exact Wilcoxon rank sum tests with Bonferroni-Holm adjustment for multiple testing (α = 0.05). RESULTS: When Optibond FL was used, partial or total replacement of phosphoric acid with tin-chloride decreased μTBS significantly. In contrast, when Clearfil SE was used, inclusion of a tin-chloride pretreatment in the adhesive procedure increased μTBS significantly. CONCLUSIONS: Tin-chloride pretreatment had a beneficial influence on the bond promoting capacity of the MDP-containing adhesive system Clearfil SE.

Analysis of polygonal cracking patterns in chloride-bearing terrains on Mars: Indicators of ancient playa settings

The ancient southern highlands on Mars (~3.5 Gyr old) contain > 600 regions that display spectral evidence in the infrared for the presence of chloride-bearing materials. Many of these locations were previously reported to display polygonal cracking patterns. We studied more than 80 of the chloride-bearing terrains using high-resolution (0.25-0.5 m/pixel) images, as well as near-infrared spectral data, to characterize the surface textures and the associated cracking patterns and mineralogies. Our study indicates that ~75% of the studied locations display polygonal cracks that resemble desiccation cracks, while some resemble salt expansion/thrust polygons. Furthermore, we detect, spectrally, the presence of smectites in association with ~30% of the studied fractured terrains. We note that smectites are a special class of swelling clay minerals that can induce formation of large desiccation cracks. As such, we suggest that the cracking patterns are indicative of the presence of smectite phyllosilicates even in the absence of spectral confirmation. Our results suggest that many chloride-bearing terrains have a lacustrine origin and a geologic setting similar to playas on Earth. Such locations would have contained ephemeral lakes that may have undergone repeated cycles of desiccation and recharging by a near-surface fluctuating water table in order to account for the salt-phyllosilicates associations. These results have notable implications for the ancient hydrology of Mars. We propose that the morphologies and sizes of the polygonal cracks can be used as paleoenvironmental, as well as lithological, indicators that could be helpful in planning future missions.

Investigations on volcanic rocks in sediment core CRP-3 from the Ross Sea, Antarctica

The petrography, mineralogy and geochemistry of volcanic and subvolcanic rocks in CRP-3 core have been examined in detail in order to characterise and to compare them with volcanic and subvolcanic rocks cropping out in the Victoria Land area, and to define the clast provenance or to establish possible volcanic activity coeval with deposition. Clasts with sizes ranging from granule to boulder show geochemical and mineralogical features comparable with those of Ferrar Supergroup rocks. They display a subalkaline affinity and compositions ranging from basalts to dacite. Three different petrographic groups with distinct textural and grain size features (subophitic, intergranular-intersertal, and glassy-hyalopilitic) are recognised and are related to the emplacement/cooling mechanism. In the sand to silt fraction, the few glass shards that have been recognised are strongly altered: however chemical analyses show they have subalkalic magmatic affinity. Mineral compositions of the abundant free clinopyroxene grains found in the core, are less affected by alteration processes, and indicate an origin from subalkaline magmas. This excludes the presence, during the deposition of CRP-3 rocks of alkaline volcanic activity comparable with the McMurdo Volcanic Group. Strong alteration of the magmatic body intruded the Beacon sandstones obliterates the original mineral assemblage. Geochemical investigations confirm that intrusion is part of the Ferar Large Igneous Province.

Mean snow accumulation rate, and mean methane sulfonate, chloride and nitrate concentration in snow pits and firn cores of Dronning Maud Land

We quantified postdepositional losses of methane sulfonate (MSA-), nitrate, and chloride at the European Project for Ice Coring in Antarctica (EPICA) drilling site in Dronning Maud Land (DML) (75°S, 0°E). Analyses of four intermediate deep firn cores and 13 snow pits were considered. We found that about 26 ± 13% of the once deposited nitrate and typically 51 ± 20% of MSA- were lost, while for chloride, no significant depletion could be observed in firn older than one year. Assuming a first order exponential decay rate, the characteristic e-folding time for MSA- is 6.4 ± 3 years and 19 ± 6 years for nitrate. It turns out that for nitrate and MSA- the typical mean concentrations representative for the last 100 years were reached after 5.4 and 6.5 years, respectively, indicating that beneath a depth of around 1.2-1.4 m postdepositional losses can be neglected. In the area of investigation, only MSA- concentrations and postdepositional losses showed a distinct dependence on snow accumulation rate. Consequently, MSA- concentrations archived at this site should be significantly dependent on the variability of annual snow accumulation, and we recommend a corresponding correction. With a simple approach, we estimated the partial pressure of the free acids MSA, HNO3, and HCl on the basis of Henry's law assuming that ionic impurities of the bulk ice matrix are localized in a quasi-brine layer (QBL). In contrast to measurements, this approach predicts a nearly complete loss of MSA-, NO3 - , and Cl-.

Major ion concentrations and chlorine isotope composition of water-soluble chloride and structurally bound chloride in DSDP/ODP serpentinized ultramafic rocks

Eight DSDP/ODP cores were analyzed for major ion concentrations and d37Cl values of water-soluble chloride (d37Clwsc) and structurally bound chloride (d37Clsbc) in serpentinized ultramafic rocks. This diverse set of cores spans a wide range in age, temperature of serpentinization, tectonic setting, and geographic location of drilled serpentinized oceanic crust. Three of the cores were sampled at closely spaced intervals to investigate downhole variation in Cl concentration and chlorine isotope composition. The average total Cl content of all 86 samples is 0.26±0.16 wt.% (0.19±0.10 wt.% as water-soluble Cl (Xwsc) and 0.09±0.09 wt.% as structurally bound Cl (Xsbc)). Structurally bound Cl concentration nearly doubles with depth in all cores; there is no consistent trend in water-soluble Cl content among the cores. Chlorine isotope fractionation between the structurally bound Cl**- site and the water-soluble Cl**- site varies from -1.08? to +1.16?, averaging to +0.21?. Samples with negative fractionations may be related to reequilibration of the water-soluble chloride with seawater post-serpentinite formation. Six of the cores have positive bulk d37Cl values (+0.05? to +0.36?); the other two cores (173-1068A (Leg-Hole) and 84-570) have negative bulk d37Cl values (-1.26? and -0.54?). The cores with negative d37Cl values also have variable Cl**-/SO4**2- ratios, in contrast to all other cores. The isotopically positive cores (153-920D and 147-895E) show no isotopic variation with depth; the isotopically negative core (173-1068A) decreases by ~1? with depth for both the water-soluble and structurally bound Cl fractions. Non-zero bulk d37Cl values indicate Cl in serpentinites was incorporated during original hydration and is not an artifact of seawater infiltration during drilling. Cores with positive d37Cl values are most likely explained by open system fractionation during hydrothermal alteration, with preferential incorporation of 37Cl from seawater into the serpentinite and loss of residual light Cl back to the ocean. Fluid / rock ratios were probably low as evidenced by the presence of water-soluble salts. The two isotopically negative cores are characterized by a thick overlying sedimentary package that was in place prior to serpentinization. We believe the low d37Cl values of these cores are a result of hydration of ultramafic rock by infiltrating aqueous pore fluids from the overlying sediments. The resulting serpentinites inherit the characteristic negative d37Cl values of the pore waters. Chlorine stable isotopes can be used to identify the source of the serpentinizing fluid and ultimately discern chemical and tectonic processes involved in serpentinization.

Chemical and Sr isotopic compositions of 3 step leachates and residues of bulk samples, zeolites, and smectites from Lower Miocene sediments at ODP Site 166-1007

Massive clinoptilolite authigenesis was observed at about 1105 meters below sea floor (mbsf) in lower Miocene wellcompacted carbonate periplatform sediments from the Great Bahama Bank [Ocean Drilling Program, ODP Leg 166, Site 1007]. The diagenetic assemblage comprises abundant zeolite crystallized within foraminifer tests and sedimentary matrix, as well as Mg smectites. In carbonate-rich deposits, the formation of the zeolite requires a supply of silica. Thus, the objective of the study is to determine the origin of the silica supply, its diagenetic evolution, and consequently the related implications on interpretation of the sedimentary record, in terms of local or global paleoceanographic change. For lack of evidence for any volcaniclastic input or traces of Si-enriched deep fluids circulation, an in situ biogenic source of silica is validated by isotopic data and chemical modeling for the formation of such secondary minerals in shallow-water carbonate sequences. Geochemical and strontium isotopic data clearly establish the marine signature of the diagenetic zeolite, as well as its contemporaneous formation with the carbonate deposition (Sr model ages of 19.6-23.2 Ma). The test of saturation for the pore fluids specifies the equilibrium state of the present mineralogical assemblage. Seawater-rock modeling specifies that clinoptilolite precipitates from the dissolution of biogenic silica, which reacts with clay minerals. The amount of silica (opal-A) involved in the reaction has to be significant enough, at least 10 wt.%, to account for the observed content of clinoptilolite occurring at the most zeolite-rich level. Modeling also shows that the observed amount of clinoptilolite (~19%) reflects an in situ and short-term reaction due to the high reactivity of primary biogenic silica (opal-A) until its complete depletion. The episodic occurrence of these well-lithified zeolite-rich levels is consistent with the occurrence of seismic reflectors, particularly the P2 seismic sequence boundary located at 1115 mbsf depth and dated as 23.2 Ma. The age range of most zeolitic sedimentary levels (biostratigraphic ages of 21.5-22 Ma) correlates well with that of the early Miocene glaciation Mi-1 and Mi-1a global events. Thus, the clinoptilolite occurrence in the shallow carbonate platform environment far from volcanogenic supply, or in other sensitive marine areas, is potentially a significant new proxy for paleoproductivity and oceanic global events, such as the Miocene events, which are usually recognized in deep-sea pelagic sediments and high latitude deposits.