The estimation of acid dissociation constants in seawater media from potentionmetric titrations with strong base. I. The ionic product of water — Kw

The various assumptions implicit in the calculation of acid dissociation constants (based on ionic medium standard states) from potentiometric titrations using a cell with liquid junction (i.e. a pH measuring cell) have been examined. It was concluded that results can be obtained having an accuracy commensurate with the experimental precision. It has been shown that although the precise composition of the medium is a function of the hydrogen ion concentration (because of the protolytic nature of some of the ions in the media, e.g., sulphate and fluoride), the effect of such variations in the medium composition can be compensated for when defining the activity of hydrogen ion on an ionic medium standard state by defining the concentration of hydrogen ion as:

where β_HSO4 and β_HF are the relevant association constants and S_T and F_T are the total concentrations of sulphate and fluoride, respectively.This approach was used to obtain values for the ionic product of water (K_W) in artificial seawater media at various temperatures and ionic strengths. These were fitted to give the equation (molal concentration units):

$\text{pK}{}_{\mathrm{w}}\text{=}\text{3441.0}\text{T}\text{+2.256-0.7091}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{(}\text{rms deviation 0.01}\text{)}$

where I is the formal ionic strength of the artificial seawater medium and T is the absolute temperature. The values obtained are in reasonable agreement with those found by previous workers.     

The dissolution of opaline silica of diatom tests in sea water

Two different series of measurements have been made of the solubilities and rates of solution in sea water of acid-washed siliceous tests of the diatomsThalassiosira decipiens andRhizosolenia hebetata. The kinetic approach was carried out on the assumption that the tests behave as identical solid spheres. If the tests were present in considerable excess over that required for saturation of the water with respect to silica, the dissolution obeyed first order reaction kinetics and its rate was proportional to the surface area of the exposed tests. When the tests were not in excess the kinetics of dissolution appeared to be more complex. This was considered to be due to a decrease in specific surface area as dissolution proceeded. An expression developed to allow for the change of surface area as a sphere dissolves offers a partial explanation of the kinetics when the tests are not present in excess.     

Kinetic studies of the rate of dissolution of silica and diatom tests in sea water

Kinetic studies have been carried out on the dissolution of 10μm beads of silica and of the siliceous tests of two species of diatoms (Thalassiosira fluviatus andSkeletonema costatum) in sea water at 10–50°C and over the pH range 6–9. At all temperatures dissolution of the biogenous silica occurred most rapidly at pH 8 and most slowly at pH 6. First order kinetics were closely followed when the silica was present in a considerable excess over that required for saturation, the rate being proportional to the area of the silica. Apparent deviation from this type of kinetics occurred when there was insufficient silica to bring about saturation. This was undoubtedly due to the progressive decrease in the surface area which takes place as the particle dissolves. Application of the rather simplistic model developed by Kamataniet al. (1980), which makes allowance for this decrease, gave a close correspondence with the data until ∼ 90% of the silica had dissolved.     

A method of alternating characteristics with application to advection-dominated environmental systems

We present a numerical method for solving a class of systems of partial differential equations (PDEs) that arises in modeling environmental processes undergoing advection and biogeochemical reactions. The salient feature of these PDEs is that all partial derivatives appear in linear expressions. As a result, the system can be viewed as a set of ordinary differential equations (ODEs), albeit each one along a different characteristic. The method then consists of alternating between equations and integrating each one step-wise along its own characteristic, thus creating a customized grid on which solutions are computed. Since the solutions of such PDEs are generally smoother along their characteristics, the method offers the potential of using larger time steps while maintaining accuracy and reducing numerical dispersion. The advantages in efficiency and accuracy of the proposed method are demonstrated in two illustrative examples that simulate depth-resolved reactive transport and soil carbon cycling.     

Regional subglacial quarrying and abrasion below hard-bedded palaeo-ice streams crossing the Shield–Palaeozoic boundary of central Canada: the importance of substrate control

Three-dimensional surface visualization models derived from high-resolution LiDAR data provide new information about the type and scale of erosional processes below Late Wisconsin palaeo-ice streams traversing the boundary between Canadian Shield crystalline rocks with offlapping Palaeozoic limestones in central Ontario. The hard bed is directly analogous to that found below ice streams in East Antarctica and East Greenland and provides insight into the effects of abrupt changes in substrate type on subglacial processes. Erosion of hard crystalline Canadian Shield rock was largely ineffectual consisting of areal abrasion of rounded whalebacks and local lee side plucking. In contrast, fast flow over the strike of gently dipping well-bedded and jointed Palaeozoic limestones cut large flow-parallel grooves and ridges akin to mega-scale glacial lineations reflecting intense abrasion below narrow streams of subglacial debris dominated by hard crystalline Shield clasts (erodents). Regionally extensive plucking of structurally weak, well-jointed and bedded limestone produced large volumes of rubbly carbonate debris leaving a 25-km-wide belt of uncontrolled hummocky rubble terrain (long known as the Dummer Moraine in Southern Ontario) some 350 km long and locally as much as 10 m thick. Subglacial plucking and abrasion under fast flowing ice were highly effective in stripping limestone cover rocks from Precambrian basement, and over many glacial cycles, may have played a role in the location and excavation of numerous large and deep lake basins around the Shield–Palaeozoic boundary zone in North America.     

Ecological Worldview as the Central Component of Environmental Concern: Clarifying the Role of the NEP

This study examines whether an ecological worldview—operationalized by the New Ecological Paradigm (NEP) Scale--serves as the source of coherence of Environmental Concern (EC). Using data on four samples from the 1992 Gallup “Health of the Planet” Survey and the 2003 and 2010 Chinese General Social Surveys, we found that in all samples not only is the NEP the most powerful predictor of EC, but it also mediates the effects of socio-demographic variables on EC as hypothesized. The results confirm that the NEP is the source of coherence of EC, making it a meaningful construct.     

The Distribution of Chadian and earliest Arundian strata in North Wales: Implications for Dinantian (Carboniferous) lithostratigraphy and palaeogeography

The late Chadian Foel Formation, previously thought to be confined to the Dyserth area of North Wales, forms a poorly exposed but persistent basal unit to much of the Dinantian crop east of the Clwydian Range, necessitating a revision of the local lithostratigraphy. The formation comprises a peritidal heterolith which, together with the lowest few metres of the overlying Llanarmon Limestone, yields microfossil assemblages diagnostic of the Eoparastaffella Cf4α Subzone. Succeeding strata, containing the lowest archaediscid foraminifera, provide the first record of Cf4β assemblages from North Wales and establish an early Arundian age for these beds. The Foel Formation was deposited as an aggradational sequence on the northern flank of St. George's Land during a pulsed transgression which began in late Chadian times. The widely recognized basal Arundian transgression is represented by the contact between the Foel Formation and overlying platform carbonates. The latter overlap the Foel Formation in the southernmost part of the Clwydian crop demonstrating, for the first time, southwards onlap on the northern side of the Bala–Bryneglwys Fault System.