Wetlands and low-gradient topography are associated with longer hydrologic transit times in Precambrian Shield headwater catchments

The estimation of hydrologic transit times in a catchment provides insights into the integrated effects of water storage, mixing dynamics, and runoff generation processes. There has been limited effort to estimate transit times in southern boreal Precambrian Shield landscapes, which are characteristically heterogeneous with surface cover including till, thin soils, bedrock outcrops, and depressional wetland features that play contrasting hydrologic roles. This study presents approximately 3.5 years of precipitation and streamflow water isotope data and estimates mean transit times (MTTs) and the young water fraction (p_y) across six small catchments in the Muskoka-Haliburton region of south-central Ontario. The main objectives were to define a typical range of MTTs for headwater catchments in this region and to identify landscape variables that best explain differences in MTTs/p_y using airborne light detection and ranging and digital terrain analysis. Of the transit time distributions, the two parallel linear reservoir and gamma distributions best describe the hydrology of these catchments, particularly because of their ability to capture more extreme changes related to events such as snowmelt. The estimated MTTs, regardless of the modelling approach or distribution used, are positively associated with the percent wetland area and negatively with mean slope in the catchments. In this landscape, low-gradient features such as wetlands increase catchment scale water storage when antecedent conditions are dryer and decrease transit times when there is a moisture surplus, which plausibly explains the increases in MTTs and mean annual runoff from catchments with significant coverage of these landscape features.     

Pc1-2 Discrete regular daytime pulsation bursts at high latitudes

A family of related Pc1-2 (0.2–10 s) discrete daytime geomagnetic pulsations is presented using pulsation data obtained at Davis, Antarctica, a typical polar-cap station. The morphological properties of IPRP and Pclb pulsation regimes, which maximize in amplitude and frequency of occurrence under the projection of the polar cusp, are examined. Furthermore, two other variations of discrete pulsation bursts yet to be named are also presented, viz IPFP (Intervals of Pulsations with Falling Period) and IPAP (Intervals of Pulsations with Alternating Period) which are observed on rare occasions. It is also suggested that the Pc1b (0.2–5 s) should be extended to incorporate Pc2b (5–10 s) which from the results in this paper are physically the same phenomenon and could be collectively classified as IPCP (Intervals of Pulsations with Constant Period).     

Controls on the chemistry of runoff from an upland peat catchment

This study uses 2 years of data from a detailed weekly water sampling programme in a 11·4 km² upland peat catchment in the Northern Pennines, UK. The sampling comprised precipitation, soil‐water samples and a number of streams, including the basin outlet. Samples were analysed for: pH, conductivity, alkalinity, Na, K, Ca, Mg, Fe, Al, Total N, SO₄, Cl and colour. Principal component analysis (PCA) was used to identify end‐members and compositional trends in order to identify controls on the development of water composition. The study showed that the direct use of PCA had several advantages over the use of end‐member mixing analysis (EMMA) as it combines an analysis of mixing and evolving waters without the assumption of having to know the compositional sources of the water. In its application to an upland peat catchment, the study supports the view that shallow throughflow at the catotelm/acrotelm boundary is responsible for storm runoff generation and shows that baseflow is controlled by cation exchange in the catotelm and mixing with a base‐rich groundwater. Copyright © 2003 John Wiley & Sons, Ltd.     

Ice‐cover variability on shallow lakes at high latitudes: model simulations and observations

A one‐dimensional thermodynamic model for simulating lake‐ice phenology is presented and evaluated. The model can be driven with observed daily or hourly atmospheric forcing of air temperature, relative humidity, wind speed, cloud amount and snowfall. In addition to computing the energy balance components, key model output includes the temperature profile at an arbitrary number of levels within the ice/snow (or the water temperature if there is no ice) and ice thickness (clear ice and snow‐ice) on a daily basis, as well as freeze‐up and break‐up dates. The lake‐ice model is used to simulate ice‐growth processes on shallow lakes in arctic, sub‐arctic, and high‐boreal forest environments. Model output is compared with field and remote sensing observations gathered over several ice seasons. Simulated ice thickness, including snow‐ice formation, compares favourably with field measurements. Ice‐on and ice‐off dates are also well simulated when compared with field and satellite observations, with a mean absolute difference of 2 days. Model simulations and observations illustrate the key role that snow cover plays on the seasonal evolution of ice thickness and the timing of spring break‐up. It is also shown that lake morphometry, depth in particular, is a determinant of ice‐off dates for shallow lakes at high latitudes. Copyright © 2003 John Wiley & Sons, Ltd.     

Europan surface phenomena

The interaction of corotating iogenic plasma with the surface of Europa in light of recent ice sputtering, experimental results, and published Voyager data has been examined. It has been found that the residual atmosphere of Europa is made up of sputtered molecular oxygen and is exospheric from the surface outwards. It was also found that if sputtering, redistribution, and escape are considered and the sulfur dioxide/water mixing ratio is held constant over a UV observing depth, the observed sulfur dioxide density on the trailing hemisphere lends support to the hypothesis that liquid water from the interior of Europa is boiling out and being deposited as a frost layer on the surface at the rate of about 0.04 μm/year.     

Middle Stone Age starch acquisition in the Niassa Rift, Mozambique

The quest for direct lines of evidence for Paleolithic plant consumption during the African Middle Stone Age has led scientists to study residues and use-wear on flaked stone tools. Past work has established lithic function through multiple lines of evidence and the spatial breakdown of use-wear and microscopic traces on tool surfaces. This paper focuses on the quantitative analysis of starch assemblages and the botanical identification of grains from flake and core tools to learn about human ecology of carbohydrate use around the Niassa woodlands, in the Mozambican Rift. The processing of starchy plant parts is deduced from the occurrence of starch assemblages that presumably got attached to stone tool surfaces by actions associated with extractive or culinary activities. Specifically, we investigate starch grains from stone tools recently excavated in northern Mozambique at the site of Mikuyu; which presumably spans the middle to late Pleistocene and represents similar sites found along the Malawi/Niassa corridor that links East, Southern, and Central Africa. Starch was extracted and processed with a diverse tool kit consisting of scrapers, cores, points, flakes, and other kinds of tools. The microbotanical data suggests consumption of seeds, legumes, caryopses, piths, underground storage organs, nuts, and mesocarps from more than a dozen families. Our data suggest a great antiquity for starch use in Africa as well as an expanded diet and intensification.     

Anoxic nitrification: Evidence from Humber Estuary sediments (UK)

Conventional understanding of the nitrogen cycle in marine sediments has changed in recent years with the discovery of an alternative pathway for ammonia oxidation via the reduction of manganese oxides (during anoxic nitrification). In anoxic sediments, the potential for manganese oxides to serve as oxidant for nitrification may be considerable yet previous work on manganese-rich sediments has suggested anoxic nitrification may not be significant. In this study, the potential for anoxic nitrification in a range of sediment types was investigated. Laboratory incubation of sediment from three sites on the Humber Estuary, a microbially diverse environment, showed anoxic accumulation of nitrate, nitrite and dinitrogen gas, with and without the addition of synthetic manganese oxides. Incubation experiments confirmed anoxic nitrification as microbially mediated, with heat-killed controls yielding negative results. The anoxic nitrification reaction significantly depleted ammonia concentrations, and occurred simultaneously with manganese-, iron- and sulphate reduction, and methanogenesis. Taken in conjunction with other studies, results suggest anoxic nitrification may not only be dependent on total manganese concentrations but on manganese dynamics. Anoxic nitrification may be explained as a non-steady state reaction, dependent on the recent stability of a sediment system. Physical perturbation of sediments may cause the redistribution and/or introduction of manganese oxides and promote anoxic nitrification. The significance and persistence of anoxic nitrification is likely to depend on the frequency and magnitude of sediment perturbation, which explains why the reaction varies so widely across studied sites, and why it may not occur in some manganese-rich sediment.     

Phthalic acid complexation and the dissolution of forsteritic glass studied via in situ FTIR and X-ray scattering

Multiple Internal Reflection Fourier Transform Infra-Red (MIR-FTIR) spectroscopy was developed and used for in situ flow-through experiments designed to study the process of organic acid promoted silicate dissolution. In tandem with the FTIR analysis, ex situ X-ray scattering was used to perform detailed analyses of the changes in the surface structure and chemistry resulting from the dissolution process. Phthalic acid and forsteritic glass that had been Chemically Vapour Deposited (CVD) onto an internal reflection element were used as reactants, and the MIR-FTIR results showed that phthalic acid may promote dissolution by directly binding to exposed Mg metal ion centers on the solid surface. Integrated infrared absorption intensity as a function of time shows that phthalic acid attachment apparently follows a t^1/2 dependence, indicating that attachment is a diffusive process. The diffusion coefficient of phthalic acid was estimated to be approximately 7 × 10⁻⁶ cm² s⁻¹ in the solution near the interface with the glass. Shifts in the infrared absorption structure of the phthalate complexed with the surface compared to the solute species indicate that phthalate forms a seven-membered ring chelate complex. This bidentate complex efficiently depletes Mg from the glass surface, such that after reaction as much as 95% of the Mg may be removed. Surface depletion in Mg causes adsorbate density to fall after an initial attachment stage for the organic ligand. In addition, the infrared analysis shows that silica in the near surface polymerizes after Mg removal, presumably to maintain charge balance. X-ray reflectivity shows that the dissolution rate of forsteritic glass at pH 4 based on Mg removal in such flow-through experiments was equal to 4 × 10⁻¹² mol cm⁻² s⁻¹ (geometric surface area normalized). Reflectivity also shows how the surface mass density decreases during reaction from 2.64 g cm⁻³ to 2.2 g cm⁻³, consistent with preferential loss of Mg from the surface. Auxiliary batch experiments with forsteritic glass films deposited onto soda glass were also completed to add further constraints to the mechanism of reaction. By combining reflectivity with diffuse scatter measurements it is shown that the primary interface changes little in terms of atomic-scale roughness even after removal of several hundred angstroms of material. These measurements unequivocally show how a dicarboxylic acid bonds to and may chelate the dissolution of a magnesium-bearing silicate. At the molecular level the solid surface retreat may best be described by a depinning model where Mg is preferentially removed and residual silica tetrahedra polymerize and act to episodically “pin” the surface.     

Tracing groundwater flow and sources of organic carbon in sandstone aquifers using fluorescence properties of dissolved organic matter (DOM)

The fluorescence properties of groundwaters from sites in two UK aquifers, the Penrith Sandstone of Cumbria and the Sherwood Sandstone of South Yorkshire, were investigated using excitation–emission matrix (EEM) fluorescence spectroscopy. Both aquifers are regionally important sources of public supply water and are locally impacted by pollution. The Penrith Sandstone site is in a rural setting while the Sherwood Sandstone site is in suburban Doncaster. Fluorescence analysis of samples from discrete sample depths in the Penrith Sandstone shows decreasing fulvic-like intensities with depth and also shows a good correlation with CFC-12, an anthropogenic groundwater tracer. Tryptophan-like fluorescence centres in the depth profile may also provide evidence of rapid routing of relatively recent applications of organic slurry along fractures. Fluorescence analysis of groundwater sampled from multi-level piezometers installed within the Sherwood Sandstone aquifer also shows regions of tryptophan-like and relatively higher fulvic-like signatures. The fluorescence intensity profile in the piezometers shows tryptophan-like peaks at depths in excess of 50 m and mirrors the pattern exhibited by microbial species and CFCs highlighting the deep and rapid penetration of modern recharge due to rapid fracture flow. Fluorescence analysis has allowed the rapid assessment of different types and relative abundances of dissolved organic matter (DOM), and the fingerprinting of different sources of organic C within the groundwater system. The tryptophan:fulvic ratios found in the Penrith Sandstone were found to be between 0.5 and 3.0 and are characteristic of ratios from sheep waste sources. The Sherwood Sandstone has the lowest ratios (0.2–0.4) indicating a different source of DOM, most likely a mixture of terrestrial and microbial sources, although there is little evidence of pollution from leaking urban sewage systems. Results from these two studies suggest that intrinsic fluorescence may be used as a proxy for, or complementary tool to, other groundwater investigation methods in helping provide a conceptual model of groundwater flow and identifying different sources of DOM within the groundwater system.