Understanding the chemistry of dental erosion.

Dental erosion is caused by repeated short episodes of exposure to acids. Dental minerals are calcium-deficient, carbonated hydroxyapatites containing impurity ions such as Na(+), Mg(2+) and Cl(-). The rate of dissolution, which is crucial to the progression of erosion, is influenced by solubility and also by other factors. After outlining principles of solubility and acid dissolution, this chapter describes the factors related to the dental tissues on the one hand and to the erosive solution on the other. The impurities in the dental mineral introduce crystal strain and increase solubility, so dentine mineral is more soluble than enamel mineral and both are more soluble than hydroxyapatite. The considerable differences in structure and porosity between dentine and enamel influence interactions of the tissues with acid solutions, so the relative rates of dissolution do not necessarily reflect the respective solubilities. The rate of dissolution is further influenced strongly by physical factors (temperature, flow rate) and chemical factors (degree of saturation, presence of inhibitors, buffering, pH, fluoride). Temperature and flow rate, as determined by the method of consumption of a product, strongly influence erosion in vivo. The net effect of the solution factors determines the overall erosive potential of different products. Prospects for remineralization of erosive lesions are evaluated.

Time to endovascular reperfusion and degree of disability in acute stroke.

OBJECTIVE Faster time from onset to recanalization (OTR) in acute ischemic stroke using endovascular therapy (ET) has been associated with better outcome. However, previous studies were based on less-effective first-generation devices, and analyzed only dichotomized disability outcomes, which may underestimate the full effect of treatment. METHODS In the combined databases of the SWIFT and STAR trials, we identified patients treated with the Solitaire stent retriever with achievement of substantial reperfusion (Thrombolysis in Cerebral Infarction [TICI] 2b-3). Ordinal numbers needed to treat values were derived by populating joint outcome tables. RESULTS Among 202 patients treated with ET with TICI 2b to 3 reperfusion, mean age was 68 (±13), 62% were female, and median National Institutes of Health Stroke Scale (NIHSS) score was 17 (interquartile range [IQR]: 14-20). Day 90 modified Rankin Scale (mRS) outcomes for OTR time intervals ranging from 180 to 480 minutes showed substantial time-related reductions in disability across the entire outcome range. Shorter OTR was associated with improved mean 90-day mRS (1.4 vs. 2.4 vs. 3.3, for OTR groups of 124-240 vs. 241-360 vs. 361-660 minutes; p < 0.001). The number of patients identified as benefitting from therapy with shorter OTR were 3-fold (range, 1.5-4.7) higher on ordinal, compared with dichotomized analysis. For every 15-minute acceleration of OTR, 34 per 1,000 treated patients had improved disability outcome. INTERPRETATION Analysis of disability over the entire outcome range demonstrates a marked effect of shorter time to reperfusion upon improved clinical outcome, substantially higher than binary metrics. For every 5-minute delay in endovascular reperfusion, 1 of 100 patients has a worse disability outcome. Ann Neurol 2015;78:584-593.

Analyses of the Erosive Effect of Dietary Substances and Medications on Deciduous Teeth.

This study aimed at analysing the erosive potential of 30 substances (drinks, candies, and medicaments) on deciduous enamel, and analyse the associated chemical factors with enamel dissolution. We analysed the initial pH, titratable acidity (TA) to pH 5.5, calcium (Ca), inorganic phosphate (Pi), and fluoride (F) concentration, and degree of saturation ((pK -pI)HAP, (pK -pI)FAP, and (pK-pI)CaF2) of all substances. Then, we randomly distributed 300 specimens of human deciduous enamel into 30 groups (n = 10 for each of the substances tested. We also prepared 20 specimens of permanent enamel for the sake of comparison between the two types of teeth, and we tested them in mineral water and Coca-Cola®. In all specimens, we measured surface hardness (VHN: Vickers hardness numbers) and surface reflection intensity (SRI) at baseline (SHbaseline and SRIbaseline), after a total of 2 min (SH2min) and after 4 min (SH4min and SRI4min) erosive challenges (60 ml of substance for 6 enamel samples; 30°C, under constant agitation at 95 rpm). There was no significant difference in SHbaseline between deciduous and permanent enamel. Comparing both teeth, we observed that after the first erosive challenge with Coca-Cola®, a significantly greater hardness loss was seen in deciduous (-90.2±11.3 VHN) than in permanent enamel (-44.3±12.2 VHN; p = 0.007), but no differences between the two types of teeth were observed after two challenges (SH4min). After both erosive challenges, all substances except for mineral water caused a significant loss in relative surface reflectivity intensity, and most substances caused a significant loss in surface hardness. Multiple regression analyses showed that pH, TA and Ca concentration play a significant role in initial erosion of deciduous enamel. We conclude that drinks, foodstuffs and medications commonly consumed by children can cause erosion of deciduous teeth and erosion is mainly associated with pH, titratable acidity and calcium concentration in the solution.

THE RELATIONSHIP BETWEEN DEGREE OF BLOOD PRESSURE REDUCTION AND MORTALITY AMONG HYPERTENSIVES IN THE HYPERTENSION DETECTION AND FOLLOW-UP PROGRAM

The relationship between degree of diastolic blood pressure (DBP) reduction and mortality was examined among hypertensives, ages 30-69, in the Hypertension Detection and Follow-up Program (HDFP). The HDFP was a multi-center community-based trial, which followed 10,940 hypertensive participants for five years. One-year survival was required for inclusion in this investigation since the one-year annual visit was the first occasion where change in blood pressure could be measured on all participants. During the subsequent four years of follow-up on 10,052 participants, 568 deaths occurred. For levels of change in DBP and for categories of variables related to mortality, the crude mortality rate was calculated. Time-dependent life tables were also calculated so as to utilize available blood pressure data over time. In addition, the Cox life table regression model, extended to take into account both time-constant and time-dependent covariates, was used to examine the relationship change in blood pressure over time and mortality.^ The results of the time-dependent life table and time-dependent Cox life table regression analyses supported the existence of a quadratic function which modeled the relationship between DBP reduction and mortality, even after adjusting for other risk factors. The minimum mortality hazard ratio, based on a particular model, occurred at a DBP reduction of 22.6 mm Hg (standard error = 10.6) in the whole population and 8.5 mm Hg (standard error = 4.6) in the baseline DBP stratum 90-104. After this reduction, there was a small increase in the risk of death. There was not evidence of the quadratic function after fitting the same model using systolic blood pressure. Methodologic issues involved in studying a particular degree of blood pressure reduction were considered. The confidence interval around the change corresponding to the minimum hazard ratio was wide and the obtained blood pressure level should not be interpreted as a goal for treatment. Blood pressure reduction was attributed, not only to pharmacologic therapy, but also to regression to the mean, and to other unknown factors unrelated to treatment. Therefore, the surprising results of this study do not provide direct implications for treatment, but strongly suggest replication in other populations. ^

Evaluation of long chain 1,14-alkyl diols in marine sediments as indicators for upwelling and temperature

Long chain alkyl diols form a group of lipids occurring widely in marine environments. Recent studies have suggested several palaeoclimatological applications for proxies based on their distributions, but also revealed uncertainties about their applicability. Here we evaluate the use of long chain 1,14-alkyl diol indices for reconstruction of temperature and upwelling conditions by comparing index values, obtained from a comprehensive set of marine surface sediments, with environmental factors like sea surface temperature (SST), salinity and nutrient concentrations. Previous cultivation efforts indicated a strong effect of temperature on the degree of saturation and the chain length distribution of long chain 1,14-alkyl diols in Proboscia spp., quantified in the diol saturation index (DSI) and diol chain length index (DCI), respectively. However, values of these indices in surface sediments show no relationship with annual mean SST of the overlying water. It remains unknown what determines the DSI, although our data suggests that it may be affected by diagenesis, while the relationship between temperature and DCI may be different for different Proboscia species. In addition, contributions of algae other than Proboscia diatoms may affect both indices, although our data provide no direct evidence for additional long chain 1,14-alkyl diol sources. Two other indices using the abundance of 1,14-diols vs. 1,13-diols and C30 1,15-diols have previously been applied as indicators for upwelling intensity at different locations. The geographical distribution of their values supports the use of 1,14 diols vs. 1,13 diols [C28 + C30 1,14-diols]/[(C28 + C30 1,13-diols) + (C28 + C30 1,14-diols)] as a general indicator for high nutrient or upwelling conditions.

(Table 1) Elemental composition, pyrite-Fe and degree of pyritisation in Upper Pliensbachian and Lower Toarcian sediments from the costal section of Yorkshire

Profiles of Mo/total organic carbon (TOC) through the Lower Toarcian black shales of the Cleveland Basin, Yorkshire, United Kingdom, and the Posidonia shale of Germany and Switzerland reveal water mass restriction during the interval from late tenuicostatum Zone times to early bifrons Zone times, times which include that of the putative Early Toarcian oceanic anoxic event. The degree of restriction is revealed by crossplots of Mo and TOC concentrations for the Cleveland Basin, which define two linear arrays with regression slopes (ppm/%) of 0.5 and 17. The slope of 0.5 applies to sediment from the upper semicelatum and exaratum Subzones. This value, which is one tenth of that for modern sediments from the Black Sea (Mo/TOC regression slope 4.5), reveals that water mass restriction during this interval was around 10 times more severe than in the modern Black Sea; the renewal frequency of the water mass was between 4 and 40 ka. The Mo/TOC regression slope of 17 applies to the overlying falciferum and commune subzones: the value shows that restriction in this interval was less severe and that the renewal frequency of the water mass was between 10 and 130 years. The more restricted of the two intervals has been termed the Early Toarcian oceanic anoxic event but is shown to be an event caused by basin restriction local to NW Europe. Crossplots of Re, Os, and Mo against TOC show similar trends of increasing element concentration with increase in TOC but with differing slopes. Together with modeling of 187Os/188Os and d98Mo, the element/TOC trends show that drawdown of Re, Os, and Mo was essentially complete during upper semicelatum and exaratum Subzone times (Mo/TOC regression slope of 0.5). Drawdown sensitized the restricted water mass to isotopic change forced by freshwater mixing so that continental inputs of Re, Os, and Mo, via a low-salinity surface layer, created isotopic excursions of up to 1.3 per mil in d98Mo and up to 0.6 per mil for 187Os/188Os. Restriction thereby compromises attempts to date Toarcian black shales, and possibly all black shales, using Re-Os chronology and introduces a confounding influence in the attempts to use d98Mo and initial 187Os/188Os for palaeo-oceanographic interpretation.

(Table 1) Sulfur isotopes, total sulfur, and degree of oxidation of basalt samples from DSDP Hole 69-504B and 70-504B

About 150 basalt samples from Hole 504B, near the Costa Rica Rift were analyzed for sulfur content and sulfur-isotope composition. The basement in Hole 504B can be divided into an upper part, which has oxidative alteration (274.5-550 m below sea floor), and a lower part, which has nonoxidative alteration (550-835 m below sea floor) (the interval from 540 to 585 meters actually is transitional). This division is reflected in both the sulfur content and the sulfurisotope composition. Oxidative alteration of basalts by sea water at low temperatures has resulted in a depletion in sulfur in the upper part of the hole (mostly less than 600 ppm S) as compared to fresh sulfur-saturated oceanic tholeiites (900-1200 ppm S). High amounts of sulfur in the lower part of the hole are a result of precipitation of secondary pyrite under non-oxidative or weakly oxidative conditions from solutions which dissolved igneous sulfides. The average sulfur-isotope composition of the primary igneous sulfides is d34S = -0.01 per mil, which is close to the assumed mantle sulfur composition (d34S = 0 per mil. Pyrite and sulfate sulfur extracted together in a separate preparation step (as "pyrite-sulfate" sulfur) indicate addition of sea-water sulfate to the upper part of the basalts. The d34S of secondary pyrite isolated by hand-picking varies between -8.0 and +5.8 per mil; the "pyrite-sulfate" sulfur (d34S = -4.8 to +10.5 per mil), as well as that of the isolated pyrite, may have originated in the precipitation of pyrite from solutions containing sulfur from the dissolution of igneous sulfides, but addition of sulfur transported by hydrothermal solutions cannot be excluded.

Composition of pore water and diagenetic carbonates of ODP Site 123-765

Degradation of organic matter in slightly organic-rich (1 wt% organic carbon) Neogene calcareous turbidites of the Argo Basin at Site 765 by sulfate reduction results in pore-water phosphate, ammonium, manganese, and carbonate alkalinity maxima. Pore-water calcium and magnesium decrease in the uppermost 100 meters below seafloor (mbsf) in response to the precipitation of calcian dolomite with an average composition of Ca1.15Mg0.83Fe0.02(CO3)2. Clear, euhedral dolomite rhombs range from <1 to 40 µm in diameter and occur in trace to minor amounts (<1-2 wt%) in Pleistocene to Pliocene sediment (62-210 mbsf) The abundance of dolomite increases markedly (2-10 wt%) in Miocene sediment (210-440 mbsf). The dolomite is associated with diagenetic sepiolite and palygorskite, as well as redeposited biogenic low-Mg calcite and aragonitic benthic foraminifers. Currently, dolomite is precipitating at depth within the pore spaces of the sediment, largely as a result of aragonite dissolution. The rate of aragonite dissolution, calculated from the pore-water strontium profile, is sufficient to explain the amount of dolomite observed at Site 765. A foraminiferal aragonite precursor is further supported by the carbon and oxygen isotopic compositions of the dolomite, which are fairly close to the range of isotopic compositions observed for Miocene benthic foraminifers. Dolomite precipitation is promoted by the degradation of organic matter by sulfate-reducing bacteria because the lower pore-water sulfate concentration reduces the effect of sulfate inhibition on the dolomite reaction and because the higher carbonate alkalinity increases the degree of saturation of the pore waters with dolomite. Organic matter degradation also results in the precipitation of pyrite and trace amounts of apatite (francolite), and the release of iron and manganese to the pore water by reduction of Fe and Mn oxides. Spherical, silt-sized aggregates of microcrystalline calcian rhodochrosite occur in trace to minor amounts in Lower Cretaceous sediment from 740 to 900 mbsf at Site 765. A negative carbon isotopic composition suggests that the rhodochrosite formed early in the sulfate reduction zone, but a depleted oxygen isotopic composition suggests that the rhodochrosite may have recrystallized at deeper burial depths.

Geochemistry and degree of organic carbon preservation in non-bioturbated, shaly sediments

Based on 13 published porewater H2S and sulphate profiles the amount of H2S escaping from non-bioturbated shales varies between some few % to 45% of the amount of bacterially generated H2S. This finding permits calculation of the original organic carbon (TOCor) content of immature nonbioturbated shales using TOC and sulphur content data. In two immature non-bioturbated sequences from Hungary (Toarcian and Oligocene) the first-order correlation between HI and TOC/TOCor was found to be stronger than that between HI and TOC, indicating that sulphate reduction was the leading process both in decrease in TOC content and degradation of kerogen source potential.

(Table 1) Sulfur isotopes, total sulfur, and degree of oxidation of basalt samples from DSDP Holes 69-504B and 70-504B

Whole-rock basalt samples from the upper half of Deep Sea Drilling Project Hole 504B have oxygen-isotope compositions typical of mid-ocean-ridge basalts which have experienced a moderate degree of low-temperature alteration by sea water. By contrast, d18O values in the lower half of the hole correspond to basalts which have experienced almost no detectable oxygen-isotope alteration. These observations suggest that the overall water/rock ratio was lower in the lower half of the drilled crust. A correlation between d18O values and 87Sr/86Sr ratios suggests that the water/rock ratio, rather than temperature variation, was the main factor determining basalt d18O values. Hydrogen-isotope data appear to be consistent with a low water/rock ratio in the lower part of the crust.

Seawater carbonate chemistry and biological processes of oysters Crassostrea virginica during experiments, 2010

Estuarine organisms are exposed to periodic strong fluctuations in seawater pH driven by biological carbon dioxide (CO2) production, which may in the future be further exacerbated by the ocean acidification associated with the global rise in CO2. Calcium carbonate-producing marine species such as mollusks are expected to be vulnerable to acidification of estuarine waters, since elevated CO2 concentration and lower pH lead to a decrease in the degree of saturation of water with respect to calcium carbonate, potentially affecting biomineralization. Our study demonstrates that the increase in CO2 partial pressure (pCO2) in seawater and associated decrease in pH within the environmentally relevant range for estuaries have negative effects on physiology, rates of shell deposition and mechanical properties of the shells of eastern oysters Crassostrea virginica (Gmelin). High CO2 levels (pH ~7.5, pCO2 ~3500 µatm) caused significant increases in juvenile mortality rates and inhibited both shell and soft-body growth compared to the control conditions (pH ~8.2, pCO2 ~380 µatm). Furthermore, elevated CO2 concentrations resulted in higher standard metabolic rates in oyster juveniles, likely due to the higher energy cost of homeostasis. The high CO2 conditions also led to changes in the ultrastructure and mechanical properties of shells, including increased thickness of the calcite laths within the hypostracum and reduced hardness and fracture toughness of the shells, indicating that elevated CO2 levels have negative effects on the biomineralization process. These data strongly suggest that the rise in CO2 can impact physiology and biomineralization in marine calcifiers such as eastern oysters, threatening their survival and potentially leading to profound ecological and economic impacts in estuarine ecosystems.

Ba distribution in surface sediments of the Southern Ocean

We present excess Ba (Baxs) data (i.e., total Ba corrected for lithogenic Ba) for surface sediments from a north-south transect between the Polar Front Zone and the northern Weddell Gyre in the Atlantic sector and between the Polar Front Zone and the Antarctic continent in the Indian sector. Focus is on two different processes that affect excess Ba accumulation in the sediments: sediment redistribution and excess Ba dissolution. The effect of these processes needs to be corrected for in order to convert accumulation rate into vertical rain rate, the flux component that can be linked to export production. In the Southern Ocean a major process affecting Ba accumulation rate is sediment focusing, which is corrected for using excess 230Th. This correction, however, may not always be straightforward because of boundary scavenging effects. A further major process affecting excess Ba accumulation is barite dissolution during exposure at the sediment-water column interface. Export production estimates derived from excess 230Th and barite dissolution corrected Baxs accumulation rates (i.e., excess Ba vertical rain rates) are of the same magnitude but generally larger than export production estimates based on water column proxies (234Th-deficit in the upper water column; particulate excess Ba enrichment in the mesopelagic water column). We believe export production values based on excess Ba vertical rain rate might be overestimated due to inaccurate assessment of the Baxs preservation rate. Barite dissolution has, in general, been taken into account by relating it to exposure time before burial depending on the rate of sediment accumulation. However, the observed decrease of excess Ba content with increasing water column depth (or increasing hydrostatic pressure) illustrates the dependence of barite preservation on degree of saturation in the deep water column in accordance with available thermodynamic data. Therefore correction for barite dissolution would not be appropriate by considering only exposure time of the barite to some uniformly undersaturated deep water but requires also that regional differences in degree of undersatuation be taken into account.