An ultrastructural study of bonding to dentin smear layers

Abstract no. 998published_or_final_versio

Optimisation of a current generation ICP-QMS and benchmarking against MC-ICP-MS spectrometry for the determination of lead isotope ratios in environmental samples

© 2018 The Royal Society of Chemistry. Novel ANOVA methodology was used to benchmark ICP-QMS against MC-ICP-MS for Pb isotope ratios, demonstrating "fitness-for-purpose" in environmental source apportionment. The precision and accuracy of lead (Pb) isotope measurements obtained from quadrupole-based mass spectrometers (ICP-QMS) are considered to be limited by a number of factors originating in different components of the instruments. In this study, experimental and instrumental protocols were optimised for determining lead isotope ratios in urban soil digests. Experimental measures included individual dilution of all samples and isotopic standards (SRM-981, NIST) to a single Pb concentration intended to produce an intensity which was high enough to negate blanks and interferences but low enough to ensure the detector operated only in pulse counting mode. Instrumental protocols included batch dead time correction, optimisation of dwell time and the number of scans employed and correction of mass discrimination by sequential application of both internal ( 203 Tl/ 205 Tl ratio) and external (SRM-981, NIST) standards. This optimised methodology was benchmarked against multi-collector mass spectrometer (MC-ICP-MS) measurements of Pb isotope ratios using replicate digest solutions of the same soil; but after these had been subjected to Pb separation using an ion-exchange procedure. On the assumption that MC-ICP-MS measurements are more accurate, small additive and multiplicative differences were observed in only the 4 th decimal place. ANOVA was used to compare the precisions of the two techniques demonstrating equal precisions c. 0.08% for 207 Pb/ 206 Pb, suggesting a sample heterogeneity limitation. By contrast, for 207 Pb/ 204 Pb, the worst-case ratio, ICP-QMS had a 10-fold poorer precision, despite negligible interference from 204 Hg, implying an instrumental limitation. The study concludes that ICP-QMS can provide valuable source apportionment information for most Pb isotope ratios but further efforts should focus on improving assay of the 207 Pb/ 204 Pb ratio

Hydration interactions: aqueous solvent effects in electric double layers

A model for ionic solutions with an attractive short-range pair interaction between the ions is presented. The short-range interaction is accounted for by adding a quadratic non-local term to the Poisson-Boltzmann free energy. The model is used to study solvent effects in a planar electric double layer. The counter-ion density is found to increase near the charged surface, as compared with the Poisson-Boltzmann theory, and to decrease at larger distances. The ion density profile is studied analytically in the case where the ion distribution near the plate is dominated only by counter-ions. Further away from the plate the density distribution can be described using a Poisson-Boltzmann theory with an effective surface charge that is smaller than the actual one.Comment: 11 Figures in 13 files + LaTex file. 20 pages. Accepted to Phys. Rev. E. Corrected typos and reference

Novel methodology for predicting the critical salt concentration of bubble coalescence inhibition

Bubble coalescence in some salt solutions can be inhibited if the salt concentration reaches a critical concentration Ccr. There are three models available for Ccr in the literature, but they fail to predict Ccr correctly. The first two models employ the van der Waals attraction power laws to establish Ccr from the discriminant of quadratic or cubic polynomials. To improve the two models, the third model uses the same momentum balance equation of the previous models but different intermolecular force generated by water hydration with exponential decaying. The third prediction for Ccr requires the experimental input for film rupture thickness and is incomplete. We show further in this paper that the third model is incorrect. We propose a novel methodology for determining C cr which resolves the mathematical uncertainties in modeling C cr and can explicitly predict it from any relevant intermolecular forces. The methodology is based on the discovery that Ccr occurs at the local maximum of the balance equation for the capillary pressure, disjoining pressure, and pressure of the Gibbs-Marangoni stress. The novel generic approach is successfully validated using nonlinear equations for complicated disjoining pressure

A lattice gas model of II-VI(001) semiconductor surfaces

We introduce an anisotropic two-dimensional lattice gas model of metal terminated II-IV(001) seminconductor surfaces. Important properties of this class of materials are represented by effective NN and NNN interactions, which result in the competition of two vacancy structures on the surface. We demonstrate that the experimentally observed c(2x2)-(2x1) transition of the CdTe(001) surface can be understood as a phase transition in thermal equilbrium. The model is studied by means of transfer matrix and Monte Carlo techniques. The analysis shows that the small energy difference of the competing reconstructions determines to a large extent the nature of the different phases. Possible implications for further experimental research are discussed.Comment: 7 pages, 2 figure

Changing nutrient cycling in Lake Baikal, the world's oldest lake

Lake Baikal, lying in a rift zone in southeastern Siberia, is the world's oldest, deepest, and most voluminous lake that began to form over 30 million years ago. Cited as the "most outstanding example of a freshwater ecosystem" and designated a World Heritage Site in 1996 due to its high level of endemicity, the lake and its ecosystem have become increasingly threatened by both climate change and anthropogenic disturbance. Here, we present a record of nutrient cycling in the lake, derived from the silicon isotope composition of diatoms, which dominate aquatic primary productivity. Using historical records from the region, we assess the extent to which natural and anthropogenic factors have altered biogeochemical cycling in the lake over the last 2,000 y. We show that rates of nutrient supply from deep waters to the photic zone have dramatically increased since the mid-19th century in response to changing wind dynamics, reduced ice cover, and their associated impact on limnological processes in the lake. With stressors linked to untreated sewage and catchment development also now impacting the near-shore region of Lake Baikal, the resilience of the lake's highly endemic ecosystem to ongoing and future disturbance is increasingly uncertain