Tidal variability in the water quality of an urbanized estuary

Tide and water quality data were collected concurrently in the Hackensack River estuary (HRE), a tidal tributary of the New York-new Jersey Harbor estuary. Harmonic analyses of tidal elevation data indicate that HRE tides are predominantly semidiurnal, though modulated by diurnal and fortnightly components. Nearly uniform tidal ranges (averaging approximately 1.6 m) were observed at three stations within the HRE. Periodogram estimates reveal significant tidal variability for the water quality parameter NH₄−N under dry-weather conditions. Lag correlation analyses associate NH₄−N concentration variations with water level fluctuations. Longitudinal profile plots for NH₄−N reveal a consistent pattern of tidal translations, with peak concentrations oscillating about a major wastewater discharger. These analyses suggest that the distribution of NH₄−N concentrations in the HRE is controlled primarily by major point source loadings and horizontal advection. A simplified, one-dimensional model is used to describe this distribution. Effects of tidal variability in masking water quality status and waak trends are also analyzed. These analyses highlight the potential importance of short-term water quality variability in tidal estuaries where concentration gradients are large.     

Mineral dissolution in the Cape Cod aquifer, Massachusetts, USA: I . Reaction stoichiometry and impact of accessory feldspar and glauconite on strontium isotopes, solute concentrations, and REY distribution

To compare relative reaction rates of mineral dissolution in a mineralogically simple groundwater aquifer, we studied the controls on solute concentrations, Sr isotopes, and rare earth element and yttrium (REY) systematics in the Cape Cod aquifer. This aquifer comprises mostly carbonate-free Pleistocene sediments that are about 90% quartz with minor K-feldspar, plagioclase, glauconite, and Fe-oxides. Silica concentrations and pH in the groundwater increase systematically with increasing depth, while Sr isotopic ratios decrease. No clear relationship between ⁸⁷Sr/⁸⁶Sr and Sr concentration is observed. At all depths, the ⁸⁷Sr/⁸⁶Sr ratio of the groundwater is considerably lower than the Sr isotopic ratio of the bulk sediment or its K-feldspar component, but similar to that of a plagioclase-rich accessory separate obtained from the sediment. The Si-⁸⁷Sr/⁸⁶Sr-depth relationships are consistent with dissolution of accessory plagioclase. In addition, solutes such as Sr, Ca, and particularly K show concentration spikes superimposed on their respective general trends. The K-Sr-⁸⁷Sr/⁸⁶Sr systematics suggests that accessory glauconite is another major solute source to Cape Cod groundwater. Although the authigenic glauconite in the Cape Cod sediment is rich in Rb, it is low in in-grown radiogenic ⁸⁷Sr because of its young Pleistocene age. The low ⁸⁷Sr/⁸⁶Sr ratios are consistent with equilibration of glauconite with seawater. The impact of glauconite is inferred to vary due to its variable abundance in the sediments. In the Cape Cod groundwater, the variation of REY concentrations with sampling depth resembles that of K and Rb, but differs from that of Ca and Sr. Shale-normalized REY patterns are light REY depleted, show negative Ce anomalies and super-chondritic Y/Ho ratios, but no Eu anomalies. REY input from feldspar, therefore, is insignificant compared to input from a K-Rb-bearing phase, inferred to be glauconite. These results emphasize that interpretation of groundwater chemistry, even in relatively simple aquifers, may be complicated by solute contributions from “exotic” accessory minerals such as glauconite. To detect such peculiarities, groundwater studies should combine the study of elemental concentration and isotopic composition of several solutes that show different geochemical behavior.     

Decoupling of As and Fe release to Bangladesh groundwater under reducing conditions. Part I: Evidence from sediment profiles

This study reexamines the notion that extensive As mobilization in anoxic groundwater of Bangladesh is intimately linked to the dissolution of Fe oxyhydroxides on the basis of analyses performed on a suite of freshly collected samples of aquifer material. Detailed sediment profiles extending to 40 to 70 m depth below the surface were obtained at six sites where local groundwater As concentrations were known to span a wide range. The sediment properties that were measured include (1) the proportion of Fe(II) in the Fe fraction leached in hot 1.2 N HCl, (2) diffuse spectral reflectance, and (3) magnetic susceptibility.In parallel with local concentrations of dissolved As ranging from <5 to 600 μg/L, Fe(II)/Fe ratios in shallow (gray) Holocene sands tended to gradually increase with depth from values of 0.3 to 0.5 to up to 0.9. In deeper (orange) aquifers of presumed Pleistocene age that were separated from shallow sands by a clay layer and contained <5 μg/L dissolved As, leachable Fe(II)/Fe ratios averaged ∼0.2. There was no consistent relation between sediment Fe(II)/Fe and dissolved Fe concentrations in groundwater in nearby wells. The reflectance measurements indicate a systematic linear relation (R² of 0.66; n = 151) between the first derivative transform of the reflectance at 520 nm and Fe(II)/Fe. The magnetic susceptibility of the shallow aquifer sands ranged from 200 to 3600 (x 10⁻⁹ m³/kg SI) and was linearly related (R² of 0.75; n = 29) to the concentrations of minerals that could be magnetically separated (0.03 to 0.79% dry weight). No systematic depth trends in magnetic susceptibility were observed within the shallow sands, although the susceptibility of deeper low-As aquifers was low (up to ∼200 × 10⁻⁹ m³/kg SI).This set of observations, complemented by incubation results described in a companion paper by van Geen et al. (this volume), suggests that the release of As is linked to the transformation of predominantly Fe (III) oxyhydroxide coatings on sand particles to Fe(II) or mixed Fe(II/III) solid phases with a flatter reflectance spectrum such as siderite, vivianite, or magnetite, without necessarily resulting in the release of Fe to groundwater. The very low As/Fe ratio of magnetically separated minerals compared to the As/Fe of bulk acid leachate (2 vs. 40 10⁻⁶, respectively) suggests that such a transformation could be accompanied by a significant redistribution of As to a mobilizable phase on the surface of aquifer particles.     

Refined relationship between the position of the fundamental OH stretching and the first overtones for clays

The aim of this paper is to determine a relationship between the wavenumbers of the first OH-stretching overtones (W_2OH) and the wavenumbers of the OH-stretching fundamentals (W_OH) to help to interpret the near-infrared (NIR) spectra. The first overtone (2OH) bands appear at wavenumbers less than twice those of the fundamental bands (OH), due to the anharmonic character of vibrations, X = W_2OH/2 - W_OH, with X being the anharmonicity constant. Talc samples with various crystal chemistries are used to solve the equation and the experimental data are well fitted with X = –85.6 cm^–1. As far as the authors are aware, it is the first time that the anharmonicity constant for the OH-stretching vibrations is determined for phyllosilicates. The anharmonicity constant remains almost unchanged for several types of clay samples. Therefore the relation, established from talc samples because their absorption bands are narrow and their wavenumber range of OH vibrations is wide, can be used for any other clay minerals.     

Subbottom acoustic and sedimentary records of past surface water–groundwater exchange through sinkhole lakes in south Georgia,U.S.A

Lake Balboa is a deep sinkhole lake in south Georgia. Subbottom acoustic profiling and long sediment cores reveal four stratigraphic units within >20 m of lacustrine fill above acoustically stratified and faulted Miocene/Pliocene overburden and basement Eocene limestone which hosts the Floridan Aquifer system (FAS). Fill consists of thin, rhythmically bedded, peaty sediments (Unit I), indicative of slow sedimentation in a shallow swamp until 13,110–12,680 cal BP, a mix of desiccated and over-consolidated clay and silty sand (Unit II) implying periodic subaerial exposure of the lake bed until 9470–9025 cal BP, and gyttja associated with a rapid 8 m rise in water level by 9120–9020 cal BP (Unit III), as well as an additional rise of 10 m to modern lake levels (Unit IV). Accumulation of nearly 4.5 m of low permeability gyttja, and higher lake levels have fundamentally changed exchange between surface water and groundwater, reducing by 40% or more the rate of vertical leakage to the FAS and increasing shallow aquifer discharge to the lake.     

High-pressure isosymmetrical phase transition in calaverite

Using density functional theory, we perform ab initio calculations of the behaviour of calaverite, AuTe₂, at high pressures. Calaverite has a distorted CdI₂ structure, that presents a pronounced two-dimensional character and a rather anisotropic response to pressure. Increasing the pressure, we predict an isosymmetrical phase transition between 55 and 60 GPa, that is accompanied by an important distortion of the structure, observed in all its geometrical parameters, especially the c lattice parameter. Relaxing the pressure, the reverse phase transition is observed between 30 and 25 GPa.     

Laboratory and case studies of thermal cycling and stored strain on the stability of selected marbles

Studies of marble panels from the exterior of two buildings document the processes leading to bowing of the material. Bowing of panels is most extensive in those areas that are exposed to direct or reflected thermal energy. The thermal anisotropic behavior of calcite results in grain-boundary separation, grain sliding and microfracturing. The resulting loss of strength is one factor leading to bowing. The development of bows further reduces the panel strength as the outer portions elongate by inelastic deformation mechanisms. Laboratory experiments cycling marble samples for over 200 cycles at three temperatures up to 107°C above room conditions show similar strength losses as the natural situation. The second factor contributing to the bowing process is the release of residual elastic strain. The strain is in part stored in the marble from its geologic history, but may also be accumulated during thermal cycling due to the properties of calcite. Marble panels have been found to bow when stored outside, but not attached to any framework, indicating that the release of residual strain is a critical factor in producing the bows.     

Deep seismic reflection profiling in the Archaean northeastern Yilgarn Craton, Western Australia: implications for crustal architecture and mineral potential

Deep seismic reflection data across the Archaean Eastern Goldfields Province, northeastern Yilgarn Craton, Western Australia, have provided information on its crustal architecture and on several of its highly mineralised belts. The seismic reflection data allow interpretation of several prominent crustal scale features, including an eastward thickening of the crust, subdivision of the crust into three broad layers, the presence of a prominent east dip to the majority of the reflections and the interpretation of three east-dipping crustal-penetrating shear zones. These east-dipping shear zones are major structures that subdivide the region into four terranes. Major orogenic gold deposits in the Eastern Goldfields Province are spatially associated with these major structures. The Laverton Tectonic Zone, for example, is a highly mineralised corridor that contains several world-class gold deposits plus many smaller deposits. Other non crustal-penetrating structures within the area do not appear to be as well endowed metallogenically as the Laverton structure. The seismic reflection data have also imaged a series of low-angle shear zones within and beneath the granite–greenstone terranes. Where the low-angle shear zones intersect the major crustal-penetrating structures, a wedge shaped geometry is formed. This geometry forms a suitable fluid focusing wedge in which upward to subhorizontal moving fluids are focused and then distributed into the nearby complexly deformed greenstones.     

Spatial correlation of deformation and mineral reaction in experimentally deformed plagioclase–olivine aggregates

Shear deformation of hot pressed plagioclase–olivine aggregates was studied in the presence and absence of mineral reaction. Experiments were performed at 900 °C, 1500 MPa, and a constant shear strain rate of 5×10⁻⁵ s⁻¹ in a solid medium apparatus. Whether the mineral reaction between plagioclase and olivine takes place or not is controlled by choosing the appropriate plagioclase composition; labradorite (An₆₀) does not react, anorthite (An₉₂) does. Labradorite–olivine aggregates deformed without reaction are very strong and show strain hardening throughout the experiment. Syndeformational reaction between olivine and anorthite causes a pronounced strain weakening. The reaction produces fine-grained opx–cpx–spinel aggregates, which accommodate a large fraction of the finite strain. Deformation and reaction are localised within a 0.5-mm-wide sample. Three representative samples were analysed for their fabric anisotropy R* and shape-preferred orientation α* (fabric angle with the shear plane) using the autocorrelation function (ACF). Fabric anisotropy can be calibrated to quantify strain variations across the sheared samples. In the deformed and reacted anorthite–olivine aggregate, there is a strong correlation between reaction progress and strain; regions of large shear strain correspond to regions of maximum reaction progress. Within the sample, the derived strain rate variations range up to almost one order of magnitude.