Prediction of solid/liquid distribution coefficients of radiocaesium in soils and sediments. Part three: a quantitative test of a KID predictive equation

An equation is presented for predicting solid/liquid distribution coefficients of radiocaesium on soils and sediments (freshwater and marine). The equation is based on the value of the radiocaesium interception potential of the illitic frayed edge sites of the system and liquid phase composition (K, NH₄ and Na). The predictive potential of the equation is tested for some 130 combinations of soil/sediment and water composition covering a three-order-of-magnitude range in K_D^137_Cs values. On average, experimental K_D^137_Cs values exceed predicted values by a factor of 1.62 ± 0.75.     

Use of solid phase characterisation and chemical modelling for assessing the behaviour of arsenic in contaminated soils

A soil, containing waste material from an industrially contaminated site, was found to be heavily contaminated with several heavy metals and As. A risk assessment for As leaching from this material has been carried out in several stages, collation and examination of historical records, solid-phase characterization and chemical modelling. The historical record indicates that the most probable source of As was arsenopyrite. However, the solid phase characterization of the soil, using X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive microanalysis (EDAX), did not yield any direct evidence for pyritic phases, although there was clear evidence of known pyrite-weathering products, such as jarosite. The relative stability of pyrite and arsenopyrite have been modelled for the range of acidity and redox potentials likely to be encountered on the site. For adsorption modelling, a surface complexation model was used to predict arsenate desorption as a function of pH. It was assumed that the principal reactive adsorbent for As was hydrous ferric oxide (HFO) and this assumption was supported by the results of direct and indirect measurements and by the mineral stability calculations. This approach was successful at predicting the increased mobility of As at increasingly alkaline conditions. The modelling predictions were supported by results from batch equilibration experiments. Thus, it was possible to link direct observations of mineralogy, mineral stability calculations and adsorption models in order to predict the mobility of As. The success of this approach was dependent on identifying the reactive phase in this particular soil and having the appropriate data required for the adsorption modelling.     

Determination of molybdenum in soils and sediments with a modified zinc dithiol procedure

Molybdenum determination, in soils and sediments, by dithiol (Stanton, 1966) is difficult when an emulsified organic layer forms and interferes with the colorimetric analysis. Addition of small quantities of acetone is suggested for clarification of the organic phase.     

Empirical estimation of magnetite/liquid distribution coefficients for some transition elements

Magnetite/liquid distribution coefficients have been calculated that are consistent with observed variations in contents of V, Sc, Cr, and Ti in lavas from Craters of the Moon lava field, Idaho. In particular, our average distribution coefficient for V (27±8) is in close agreement with that determined experimentally at the temperature and oxygen fugacity appropriate for crystallization of these lavas. Although this value is not very precise, it shows that V contents of at least some calcalkaline series are consistent with generation of andesitic and related magmas from basaltic parental magmas by crystal fractionation, involving removal of appreciable amounts of magnetite.Current address: Geology Department, Rice University. Houston, Texas 77001, USA     

Determination of variables in the prediction of strontium distribution coefficients for selected sediments

Idaho State University and the US Geological Survey, in cooperation with the US Department of Energy, conducted a study to determine and evaluate strontium distribution coefficients (K_ds) of subsurface materials at the Idaho National Engineering and Environmental Laboratory (INEEL). The K_ds were determined to aid in assessing the variability of strontium K_ds and their effects on chemical transport of strontium-90 in the Snake River Plain aquifer system. Data from batch experiments done to determine strontium K_ds of five sediment-infill samples and six standard reference material samples were analyzed by using multiple linear regression analysis and the stepwise variable-selection method in the statistical program, Statistical Product and Service Solutions, to derive an equation of variables that can be used to predict strontium K_ds of sediment-infill samples. The sediment-infill samples were from basalt vesicles and fractures from a selected core at the INEEL; strontium K_ds ranged from ~201 to 356 ml g^-1. The standard material samples consisted of clay minerals and calcite. The statistical analyses of the batch-experiment results showed that the amount of strontium in the initial solution, the amount of manganese oxide in the sample material, and the amount of potassium in the initial solution are the most important variables in predicting strontium K_ds of sediment-infill samples.     

Aqueous and solid phase arsenic speciation in the sediments of a contaminated wetland and riverbed

Mobility of As in the environment is controlled by its association with solid phases through adsorption and co-precipitation. To elucidate the mobilization potential of As deposited in wetland and riverbed sediments of the Wells G & H wetland in Woburn, MA as the result of decades of industrial activity, As retention mechanisms were inferred from aqueous and solid phase geochemical measurements of sediment cores. Testing included a sequential extraction method designed for and standard-tested with As phases and pE/pH equilibrium modeling. The uppermost sediments in the Wells G & H wetland contain elevated concentrations of both dissolved and solid phase As (up to 2,000 μg/L and 15,000 μg/g, respectively) and a maximum concentration between 30 and 40 cm depth. Measurements obtained in this study suggested that As in the wetland sediments was predominantly adsorbed, likely onto amorphous Fe (hydr)oxide phases and mixed valence Fe phases. In the riverbed sediments, however, a relatively greater proportion of the solid As was associated with more reduced and crystalline phases, and adsorbed As was more likely associated with Al oxide or secondary reduced Fe phases. pH–pe modeling of the Fe–As–S system was consistent with observations. The association of As with more oxidized phases in the wetland compared with the riverbed sediments may result from a combination of plant activities, including evapotranspiration-driven water table depression and/or root oxygenation.     

The kinetics of nucleation of solid solutions from aqueous solutions: a new model for calculating non-equilibrium distribution coefficients

The nucleation kinetics of binary solid solutions, with general formula B_xC_1−xA, crystallising from aqueous solution can be described using a generalised expression for the nucleation rate: the function, J(x), in which supersaturation, interfacial free energy and other parameters of the classical nucleation rate equation are considered as functions of the solid composition. As an example, we studied the behaviour of such J(x) functions for the case of the (Ba,Sr)SO₄ and (Ba,Sr)CO₃ solid solutions. J(x) functions are very sensitive to slight changes in the composition of the aqueous solution, which result in strong modifications of the nucleation kinetics. The implications of the relationship between supersaturation and nucleation rate functions for the general nucleation behaviour in solid solution-aqueous solution (SS-AS) systems are discussed. Finally, we present a method for constructing non-equilibrium Roozeboom diagrams based on the nucleation kinetics in SS-AS systems. Our Roozeboom diagrams calculated for different departures from equilibrium conditions are consistent with previous experimental work and they can be used to predict actual distribution coefficients.     

Metal contamination and solid phase partitioning of metals in the stream and bottom sediments in a reservoir receiving mine drainage

This study was conducted to assess the anthropogenic impact on metal concentrations in the bottom sediments of the Juam reservoir, Korea, and in stream sediments in its catchment, and to estimate the potential mobility of selected metals (Fe, Mn, Cu, Ni, Pb and Zn) using sequential extraction. A comparison of the metal concentrations in the stream sediments with mean background values in sediments collected from first- or second-order creeks shows that Pb, Cu and Ni are the most affected by anthropogenic inputs. The ²⁰⁶Pb/²⁰⁷Pb ratios of the bottom and core sediments (means: 1.2320 ± 0.0502 and 1.2212 ± 0.0040, respectively) suggest that Pb contamination is mainly due to the waste discharge of abandoned coal and metal mines rather than industrial and airborne sources. Considering the proportion of metals bound to the exchangeable, carbonate and reducible fractions, the comparative mobility of metals is suggested to decrease in the order Mn > Pb > Zn > Ni > Fe ≫ Cu.     

Calcium distribution in soils and stream sediments in Istria (Croatia) and the Slovenian littoral

For experimental geochemical mapping soil was sampled in 5×5 km regular grid in Istria and the Slovenian littoral (Croatia and Slovenia). The territory consists predominantly of karstified limestones and dolomites, and of flysch beds exposed in two basins, Istrian and Brkini. In addition to soil, stream sediment was also collected in the flysh area. Sampling was performed according to an analysis of variance design that permitted one to estimate the effects of the sample medium, geographic position, sampling error and analytical error. The analysis of variance of chemical variables indicated that soil and stream sediment as sampling media lead to similar results in producing geochemical maps. The largest differences with respect to the lithologic substrate of soil is indicated by calcium. As shown by the geochemical map, calcium in soil is high on the Istrian flysch beds, and low on limestones as well as on the flysch beds of the Brkini basin. The two soils also differ in mineralogy. The reason for this difference seems to lie in soil genesis on limestone and on flysch, and in the variable calcium content of flysch beds. The results of Q-mode factor analysis confirmed the adherence of soil and stream sediment of the two flysch basins to two differing groups. This difference was discovered by geochemical mapping. The hypothesis of differing calcium content in the rocks of the two basins was confirmed by the investigation of fresh and weathered rocks and soils in eight profiles sampled in the Brkini and Istrian flysch basin. It was found that the sandstone and calcarenitic samples from the Istrian basin contain an average factor of 3.5 more Ca than those of the investigated Brkini basin, and the samples of Istrian marls 4 times more Ca than those of the Brkini siltstones. Furthermore, the investigated weathered rocks and soils that originated from these rocks in the Istrian basin contain considerably more Ca than in the Brkini basin. In comparison with sandstone and siltstone samples of the Brkini basin, sandstone, calcarenite and marl samples of the Istrian flysch basin contain less clay minerals, quartz and feldspars and more calcite.     

An approach to characterisation of multi-scale pore geometry and correlation with moisture storage and transport coefficients in cement-stabilised soils

An experimental approach to the characterisation of the complex, multi-scale pore geometry in cement-stabilised soils is presented, in which the pore size distribution inclusively spans at least six orders of magnitude from ~3 nm up to >3 mm. These most likely result from the combined effects of granular inter-particle packing, clay/cement clothing and bridging effects, cement hydration and clay/cement pozzolanic reactions, and alteration of larger pore geometries as a result of solid mass mobilisation and transport following capillary wetting/drying regimes. Experimental data are presented and were obtained through a combination of X-ray computed tomography, mercury intrusion porosimetry and N₂ physisorption supported by ‘wet mode’ environmental scanning electron microscopy. Data strongly suggest that macropore/capillary pore size distribution, mean pore size, sorptivity and transport coefficients are a function of particle size distribution (when compaction energy is constant). Mesopore size distribution, which dominates hygric sorption/desorption behaviour, occurs within the clay/cement matrix and also appears to be strongly influenced by the particle size distribution of the granular phase. All other factors being equal, manipulation of granular particle size distribution can be used to engineer the hygric (vapour) and capillary (liquid) potentials and also the fluid transport coefficients of these materials.     

Trace element cycling in a subterranean estuary: Part 1. Geochemistry of the permeable sediments

Subterranean estuaries are characterized by the mixing of terrestrially derived groundwater and seawater in a coastal aquifer. Subterranean estuaries, like their river water-seawater counterparts on the surface of the earth, represent a major, but less visible, hydrological and geochemical interface between the continents and the ocean. This article is the first in a two-part series on the biogeochemistry of the subterranean estuary at the head of Waquoit Bay (Cape Cod, MA, USA). The pore-water distributions of salinity, Fe and Mn establish the salt and redox framework of this subterranean estuary. The biogeochemistry of Fe, Mn, P, Ba, U and Th will be addressed from the perspective of the sediment composition. A second article will focus on the groundwater and pore-water chemistries of Fe, Mn, U and Ba.Three sediment cores were collected from the head of Waquoit Bay where the coastal aquifer consists of permeable sandy sediment. A selective dissolution method was used to measure the concentrations of P, Ba, U and Th that are associated with “amorphous (hydr)oxides of iron and manganese” and “crystalline Fe and Mn (hydr)oxides.” The deeper sections of the cores are characterized by large amounts of iron (hydr)oxides that are precipitated onto organic C-poor quartz sand from high-salinity pore waters rich in dissolved ferrous iron. Unlike Fe (hydr)oxides, which increase with depth, the Mn (hydr)oxides display midcore maxima. This type of vertical stratification is consistent with redox-controlled diagenesis in which Mn (hydr)oxides are formed at shallower depths than iron (hydr)oxides. P and Th are enriched in the deep sections of the cores, consistent with their well-documented affinity for Fe (hydr)oxides. In contrast, the downcore distribution of Ba, especially in core 3, more closely tracks the concentration of Mn (hydr)oxides. Even though Mn (hydr)oxides are 200-300 times less abundant than Fe (hydr)oxides in the cores, Mn (hydr)oxides are known to have an affinity for Ba which is many orders of magnitude greater than iron (hydr)oxides. Hence, the downcore distribution of Ba in Fe (hydr)oxide rich sediments is most probably controlled by the presence of Mn (hydr)oxides. U is enriched in the upper zones of the cores, consistent with the formation of highly reducing near-surface sediments in the intertidal zone at the head of the Bay. Hence, the recirculation of seawater through this type of subterranean estuary, coupled with the abiotic and/or biotic reduction of soluble U(VI) to insoluble U(IV), leads to the sediments acting as a oceanic net sink of U. These results highlight the importance of permeable sediments as hosts to a wide range of biogeochemical reactions, which may be impacting geochemical budgets on scales ranging from coastal aquifers to the continental shelf.     

Trends in the solid phase partitioning of metals in the Thames Estuary sediments during recent decades

A sequential extraction method was employed to extract the metals Al, Ag, Cd, Co, Cr, Cu, Pb, Fe, Li, Mn, Ni, and Zn from a 10-m sediment core taken from the Tilbury Basin on the Thames Estuary. Characteristics of the observed metal partitioning distributions were attributed primarily to the composition of the estuarine waters at the time of deposition. For some metals, a decrease in the bulk sediment metal concentrations from a depth of ?6.59 m ODN to the surface was also observed in one of the solid phases. This was the case for Cr, Cu, and Pb extracted from the organic phase and for Zn extracted from the carbonate phase. This decrease in sediment concentrations is thought to reflect reported improvements to water quality in this region of the Thames Estuary in the early 1960s, following updating of major sewage treatment works (STW) approximately 20 km upstream. These findings give an indication of the influence of estuarine inputs from STW on metal partitioning distributions. The order of mobility for the metals of environmental concern was Cd>Ag>Cr>Ni, Zn>Co, Cu, Pb. for Cd and Ag there was a tendency to partition towards the exchangeable phase, both at the surface and at depth, which indicates the potential for long-term leaching of these metals from the sediments.     

Finite element formulation and algorithms for unsaturated soils. Part I: Theory

This paper presents a complete finite‐element treatment for unsaturated soil problems. A new formulation of general constitutive equations for unsaturated soils is first presented. In the incremental stress–strain equations, the suction or the pore water pressure is treated as a strain variable instead of a stress variable. The global governing equations are derived in terms of displacement and pore water pressure. The discretized governing equations are then solved using an adaptive time‐stepping scheme which automatically adjusts the time‐step size so that the integration error in the displacements and pore pressures lies close to a specified tolerance. The non‐linearity caused by suction‐dependent plastic yielding, suction‐dependent degree of saturation, and saturation‐dependent permeability is treated in a similar way to the elastoplasticity. An explicit stress integration scheme is used to solve the constitutive stress–strain equations at the Gauss point level. The elastoplastic stiffness matrix in the Euler solution is evaluated using the suction as well as the stresses and hardening parameters at the start of the subincrement, while the elastoplastic matrix in the modified Euler solution is evaluated using the suction at the end of the subincrement. In addition, when applying subincrementation, the same rate is applied to all strain components including the suction. Copyright © 2003 John Wiley & Sons, Ltd.     

Sequential extraction procedure in columns. Part 1: Development and description of a new method

A sequential extraction procedure was carried out in columns using reagents that are known to be reliable from batch tests. The intention was to distinguish between different chemical forms of iron and heavy metals in samples from reduced porous aquifers, which demands anaerobic conditions for the extraction procedure and the determination of small amounts of reactive mineral phases in a quartz dominated sediment system. By means of the developed method, anaerobic conditions can be guaranteed in the columns, which could not be realized to full satisfaction in batch tests that were carried out in a glove box. In order to distinguish between the fractions that were water soluble, exchangeable, bound to carbonates and bound to hydroxides, different reagents were pumped through the sediments and sampled after passage of the columns. Sediment samples of 10 kg each were investigated in this way. The extraction steps were known to be complete when analyses revealed that no further major and trace elements were leached out of the columns. This approach enabled well-adjusted amounts of reagents to be used. By means of the sequential extraction procedure in columns the composition of even small amounts of reactive mineral phases can be determined successfully, which contributes to a deeper understanding of the hydrogeochemical processes in aquifers. In batch tests this accuracy cannot be reached because of the surplus of the extraction solution in relation to the amount of sediment (higher solution-sediment ratio). Furthermore, larger samples are much more representative of the composition of the aquifers than smaller ones and the heterogeneity of the sediment does not limit the accuracy of the results as much as in batch tests. In addition, the technique of flushing sediment in a column is much more typical for the situation in an aquifer than suspending a few grams of a sample in the extracting reagents in batch extraction tests. In order to demonstrate the methodical improvements and field applications, the newly developed method was used to investigate the changing binding forms and mobility of iron and trace metals in samples from a lignite overburden dump, which are influenced by pyrite oxidation processes (acidification) followed by the addition of crushed limestone (neutralization) (see "Sequential extraction procedure in columns. Part 2: Application of a new method").     

Finite element formulation and algorithms for unsaturated soils. Part II: Verification and application

The finite‐element formulation and integration algorithms developed in Part I are used to analyse a number of practical problems involving unsaturated and saturated soils. The formulation and algorithms perform well for all the cases analysed, with the robustness of the latter being largely insensitive to user‐defined parameters such as the number of coarse time steps and error control tolerances. The efficiency of the algorithms, as measured by the CPU time consumed, does not depend on the number of coarse time steps, but may be influenced by the error control tolerances. Based on the analyses presented here, typical values for the error control tolerances are suggested. It is also shown that the constitutive modelling framework presented in Part I can, by adjusting one constitutive equation and one or two material parameters, be used to simulate soils that expand or collapse upon wetting. Treating the suction as a strain variable instead of a stress variable proves to be an efficient and robust way of solving suction‐dependent plastic yielding. Moreover, the concept of the constitutive stress is a particularly convenient way of handling the transition between saturation and unsaturation. Copyright © 2003 John Wiley & Sons, Ltd.     

Distributions of branched GDGTs in soils and lake sediments from western Uganda: Implications for a lacustrine paleothermometer

Bacterially produced branched glycerol dialkyl glycerol tetraethers (GDGTs) are ubiquitous in soils and lake sediments and can potentially be used to reconstruct past temperatures. In lakes, however, it is still unclear if these compounds are derived from eroded soils or if they are produced in situ. To better understand environmental controls on the distributions of these compounds and the sources of branched GDGTs to lake sediments, we compare branched GDGT distributions and concentrations in lake sediments and catchment soils within a 3600 m altitudinal transect in western Uganda. Reconstructed mean annual air temperature (MAAT), determined from the degree of methylation (MBT) and cyclisation (CBT) of branched GDGTs in soils, decreases with increasing altitude, as is expected from the air temperature gradient in our transect. However, we observe significant offsets between observed and reconstructed temperatures in soils from wet, high elevation soils but not in most dry, low elevation soils. Branched GDGT distributions differ significantly between lake sediments and soils at all elevations, with greater differences at low elevations than at high elevations. These data support previous hypotheses that branched GDGTs are produced in situ in lakes and suggest that the abundance of water in soil environments may play a role in controlling the distribution of branched GDGTs. While branched GDGTs in lacustrine sediments can be used to reconstruct temporal temperature variations in lakes, we urge caution in utilizing this proxy in lacustrine systems with high soil loadings, especially if there is evidence of changing clastic fluxes through time.     

Magnetic characterisation and correlation of a Younger Dryas tephra in North Atlantic marine sediments

A technique for identifying non‐visible basaltic tephra‐rich horizons of Younger Dryas (YD)/Greenland Stadial (GS) 1 age in northeast Atlantic sediments using rapid, non‐destructive magnetic measurements is presented. Three high‐resolution marine sediment cores have been studied in an E–W transect across the Hebridean margin: St Kilda Basin (MD95‐2007), Barra Fan (MD95‐2006) and Rockall Trough (MD04‐2822). Magnetic susceptibilities and remanent magnetisations were measured at contiguous 1 cm resolution on bulk sediments. In all three cores, an interval with higher proportions of hard magnetic minerals coincides with a clearly defined peak in basaltic tephra shard (>250 µm) counts, which can be constrained to the early part of the YD/GS1 based on faunal climate proxies. Electron microprobe analyses of the magnetically distinct basaltic tephra interval, in all three cores, displays the same major element geochemistry as published for the Vedde basaltic (I Tab. 1), i.e. sourced from the Icelandic volcano Katla. The identification of transitional alkalic basaltic tephras within marine sediments could potentially be facilitated by magnetic analysis as a useful chronostratigraphic screening tool. Copyright © 2009 John Wiley & Sons, Ltd.     

Analytical and computational procedure for solving the consolidation problem of layered soils

One‐dimensional consolidation analysis of layered soils conventionally entails solving a system of differential equations subject to the flow conditions at the bounding upper and lower surfaces, as well as the continuity conditions at the interface of every pair of contiguous layers. Formidable computational efforts are required to solve the ensuing transcendental equations expressing the matching conditions at the interfaces, using this method. In this paper, the jump discontinuities in the flow parameters upon crossing from one layer to the other have been systematically built into a single partial differential equation governing the space–time variation of the excess pore pressure in the entire composite medium, by the use of the Heaviside distribution. Despite the presence of the discontinuities in the coefficients of the differential equation, a closed‐form solution in the sense of an infinite generalized Fourier series is obtained, in addition to which is the development of a Green's function for the differential problem. The eigenfunctions of the composite medium are the coordinate functions of the series, obtained computationally through the application of the extended equations of Galerkin. The analysis has been illustrated by solving the consolidation problem of a four‐layer composite, and the results obtained agree very well with the results obtained by previous researchers. Copyright © 2013 John Wiley & Sons, Ltd.