Distribution coefficients of Eu and Sr for plagioclase-liquid and clinopyroxene-liquid equilibria in oceanic ridge basalt: an experimental study

The distribution coefficients of Eu and Sr for plagioclase-liquid and clinopyroxene-liquid pairs as a function of temperature and oxygen fugacity were experimentally investigated using an oceanic ridge basalt enriched with Eu and Sr as the starting material. Experiments were conducted between 1190° and 1140°C over a range of oxygen fugacities between 10^?8 and 10^?14 atm.The molar distribution coefficients are given by the equations: log^PL_Sr = 7320/T ? 4.62logK^CPX_Sr = 18020/T ? 13.10. Similarly, the weight fraction distribution coefficients are given by the equations: logD^PL_Sr = 6570/T ? 4.30logD^CPX_Sr = 18434/T ? 13.62.Although the mole fraction distribution coefficients have a smaller dependence on bulk composition than do the weight fraction distribution coefficients, they are not independent of bulk composition, thereby restricting the application of these experimental results to rocks similar to oceanic ridge basalts in bulk composition.Because the Sr distribution coefficients are independent of oxygen fugacity, they may be used as geothermometers. If the temperature can be determined independently — for example, with the Sr distribution coefficients, the Eu distribution coefficients may be used as oxygen geobarometers. Throughout the range of oxygen fugacities ascribed to terrestrial and lunar basalts, plagioclase concentrates Eu but clinopyroxene rejects Eu.     

Paragenesis of “box-work geodes”, Tampa Bay, Florida

An unusual suite of silicified rocks was excavated during a recent harbour-deepening project in Tampa Bay, Florida. These rocks, which we have termed “box-work geodes”, are composed of convoluted, intersecting silica walls enclosing cavities which are either voids or filled with relatively pure monoclinic palygorskite. The “box-work geodes” are interpreted as having formed in shallow lagoonal environments, similar to the Coorong Lagoon of South Australia. Synaeresis of syngenetic palygorskite was followed by opal deposition and case hardening of the material. Subsequent chemical deposition of chalcedony, megacrystalline quartz, barite, and calcite on the void facing walls indicates an open chemical system.

The existence of opal saturated lagoons, as inferred from the “box-work geodes”, suggests that much of the replacement chert, porcelanite, and silicified fossils in the Tertiary deposits of peninsular Florida formed in the shallow subsurface. Subsequent weathering of carbonates and clays not encapsulated in the box works has resulted in formation of a green montmorillonite residual clay bed.     

Holocene alluvial stratigraphy in the upper Susquehanna River Basin, New York

Two alluvial terraces and the present flood plain were studied at two locations along the Susquehanna and Unadilla Rivers in south-central New York state. They have formed since deglaciation and incision of the stream channels into the valley train deposits. The higher terrace has noncumulative soil profiles with well-developed color B horizons predominantly of silt loam and very fine sandy loam. The terrace is weathered to a degree similar to nearby glacial outwash terraces that have caps of similarly textured sediments. Incision that produced the terrace occurred before 9705 ± 130 yr B.P. The lower terrace is characterized by relatively thick, vertical-accretion deposits of silt loam that contain sequences of thin, buried A, color B, and C horizons. They were formed between about 3240 ± 110 (¹⁴C data of soil humin) and 235 ± 80 yr B.P. Deposits above the 235 ± 80 yr B.P. stratum are unweathered. The soil stratigraphy and ¹⁴C dates of soil humin from buried A horizons are surprisingly well correlated between sites. Most sediments of the present flood plain have been deposited since 1120 ± 80 yr B.P. Incipient A horizons and oxidation of inherited organic matter in the subsoil are the only evidence of pedogenesis in the flood-plain deposits that are older than 275 ± 80 yr B.P. The most recent flood-plain fill deposited since then is unaltered. These youngest sediments of the flood plain along with the youngest veneer of vertical-accretion deposits on the lowest terrace are associated with an increased rate of deposition largely attributable to clearing of the forests by settlers, beginning in the late 1700s. Comparison of the alluvial stratigraphy with the radiocarbon-dated pollen stratigraphy of southwestern New York (Miller 1973) reveals some apparent time correlations between alluvial events and vegetation changes. This gives reason to speculate that climatic change or forest catastrophes such as disease or drought are causes of some of the alluvial events.     

Deltaic sedimentation in the Devonian of Western Libya

Middle and Upper Devonian deposits from the Aouinet Ouenine Formation in the southern Ghadames Basin of western Libya provide a well exposed example of a deltaic complex containing both progradational and transgressive facies. Progradational facies comprise both laterally accreting and incised distributary channels overlying prodelta deposits. Also present is a progradational beach environment showing build-up from an offshore shelf through nearshore shelf to shoreface and foreshore sub-environments. Over-lying these progradational facies are transgressive tidal-flat, washover-fan, foreshore and nearshore deposits.The characteristics and interrelationships of the different facies are explained by two sedimentation models: progradational facies existed contemporaneously during phases of active sediment supply whereas the transgressive facies existed contemporaneously during periods of diminished or absent detrital influx.     

Cu(II) adsorption at the calcite-water interface in the presence of natural organic matter: Kinetic studies and molecular-scale characterization

We have characterized the adsorption of Suwannee River humic acid (SRHA) and Cu(II) on calcite from preequilibrated solutions at pH 8.25. Sorption isotherms of SRHA on calcite follow Langmuir-type behavior at SRHA concentrations less than 15 mg C L⁻¹, whereas non-Langmuirian uptake becomes evident at concentrations greater than 15 mg C L⁻¹. The adsorption of SRHA on calcite is rapid and mostly irreversible, with corresponding changes in electrostatic properties. At pH 8.25, Cu(II) uptake by calcite in the presence of dissolved SRHA decreases with increasing dissolved SRHA concentration, suggesting that formation of Cu-SRHA aqueous complexes is the primary factor controlling Cu(II) sorption at the calcite surface under the conditions of our experiments. We also observed that surface-bound SRHA has little influence on Cu(II) uptake by calcite, suggesting that Cu(II) coordinates to calcite surface sites rather than to surface-bound SRHA.Cu K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) spectroscopic results show that the local coordination of Cu adsorbed at the calcite surface is very similar in the presence and absence of SRHA. Ca backscatterers at ∼3.90 Å indicate that Cu(II) forms tetragonally distorted inner-sphere adsorption complexes in both binary and ternary systems. Subtle differences in the XANES and EXAFS between binary sorption samples and ternary sorption samples, however, prevent us from ruling out the formation of ternary Cu-SRHA surface complexes. Our findings demonstrate that SRHA plays an important role in controlling the fate and transport of Cu(II) in calcite-bearing systems.     

Importance of climate,forest fires and human population size in the Holocene boreal forest composition change in northern Europe

The relative importance of climate, forest fires and human population size on long‐term boreal forest composition were statistically investigated at regional and local scales in Fennoscandia. We employ pollen data from lakes, reflecting regional vegetation, and small forest hollows, reflecting local vegetation, from Russia, Finland and Sweden to reconstruct the long‐term forest composition. As potential drivers of the Holocene forest dynamics we consider climate, generated from a climate model and oxygen isotope data, past forest fires generated from sedimentary charcoal data and human population size derived from radiocarbon dated archaeological findings. We apply the statistical method of variation partitioning to assess the relative importance of these environmental variables on long‐term boreal forest composition. The results show that climate is the main driver of the changes in Holocene boreal forest composition at the regional scale. However, at the local scale the role of climate is relatively small. In general, the importance of forest fires is low both at regional and local scales. The fact that both climate and forest fires explain relatively small proportions of variation in long‐term boreal vegetation in small forest hollow records demonstrates the complexity of factors affecting stand‐scale forest dynamics. The relative importance of human population size was low in both the prehistorical and the historical time periods. However, this is the first time that this type of data has been used to statistically assess the importance of human population size on boreal vegetation and the spatial representativeness of the data may cause bias to the analysis.     

Zircon M127 – A Homogeneous Reference Material for SIMS U–Pb Geochronology Combined with Hafnium,Oxygen and,Potentially, Lithium Isotope Analysis

In this article, we document a detailed analytical characterisation of zircon M127, a homogeneous 12.7 carat gemstone from Ratnapura, Sri Lanka. Zircon M127 has TIMS‐determined mean U–Pb radiogenic isotopic ratios of 0.084743 ± 0.000027 for ²⁰⁶Pb/²³⁸U and 0.67676 ± 0.00023 for ²⁰⁷Pb/²³⁵U (weighted means, 2s uncertainties). Its ²⁰⁶Pb/²³⁸U age of 524.36 ± 0.16 Ma (95% confidence uncertainty) is concordant within the uncertainties of decay constants. The δ¹⁸O value (determined by laser fluorination) is 8.26 ± 0.06‰ VSMOW (2s), and the mean ¹⁷⁶Hf/¹⁷⁷Hf ratio (determined by solution ICP‐MS) is 0.282396 ± 0.000004 (2s). The SIMS‐determined δ⁷Li value is ?0.6 ± 0.9‰ (2s), with a mean mass fraction of 1.0 ± 0.1 μg g^?1 Li (2s). Zircon M127 contains ~ 923 μg g^?1 U. The moderate degree of radiation damage corresponds well with the time‐integrated self‐irradiation dose of 1.82 × 10¹⁸ alpha events per gram. This observation, and the (U–Th)/He age of 426 ± 7 Ma (2s), which is typical of unheated Sri Lankan zircon, enable us to exclude any thermal treatment. Zircon M127 is proposed as a reference material for the determination of zircon U–Pb ages by means of SIMS in combination with hafnium and stable isotope (oxygen and potentially also lithium) determination.     

Response of low‐angle dunes to variable flow

Current understanding of bedform dynamics is largely based on field and laboratory observations of bedforms in steady flow environments. There are relatively few investigations of bedforms in flows dominated by unsteadiness associated with rapidly changing flows or tides. As a consequence, the ability to predict bedform response to variable flow is rudimentary. Using high‐resolution multibeam bathymetric data, this study explores the dynamics of a dune field developed by tidally modulated, fluvially dominated flow in the Fraser River Estuary, British Columbia, Canada. The dunes were dominantly low lee angle features characteristic of large, deep river channels. Data were collected over a field ca 1·0 km long and 0·5 km wide through a complete diurnal tidal cycle during the rising limb of the hydrograph immediately prior to peak freshet, yielding the most comprehensive characterization of low‐angle dunes ever reported. The data show that bedform height and lee angle slope respond to variable flow by declining as the tide ebbs, then increasing as the tide rises and the flow velocities decrease. Bedform lengths do not appear to respond to the changes in velocity caused by the tides. Changes in the bedform height and lee angle have a counterclockwise hysteresis with mean flow velocity, indicating that changes in the bedform geometry lag changes in the flow. The data reveal that lee angle slope responds directly to suspended sediment concentration, supporting previous speculation that low‐angle dune morphology is maintained by erosion of the dune stoss and crest at high flow, and deposition of that material in the dune trough.     

Spatial and temporal constraints on regional-scale groundwater flow in the Pampa del Tamarugal Basin,Atacama Desert,Chile

Aquifers within the Pampa del Tamarugal Basin (Atacama Desert, northern Chile) are the sole source of water for the coastal city of Iquique and the economically important mining industry. Despite this, the regional groundwater system remains poorly understood. Although it is widely accepted that aquifer recharge originates as precipitation in the Altiplano and Andean Cordillera to the east, there remains debate on whether recharge is driven primarily by near-surface groundwater flow in response to periodic flood events or by basal groundwater flux through deep-seated basin fractures. In addressing this debate, the present study quantifies spatial and temporal variability in regional-scale groundwater flow paths at 20.5°S latitude by combining a two-dimensional model of groundwater and heat flow with field observations and δ¹⁸O isotope values in surface water and groundwater. Results suggest that both previously proposed aquifer recharge mechanisms are likely influencing aquifers within the Pampa del Tamarugal Basin; however, each mechanism is operating on different spatial and temporal scales. Storm-driven flood events in the Altiplano readily transmit groundwater to the eastern Pampa del Tamarugal Basin through near-surface groundwater flow on short time scales, e.g., 10⁰–10¹ years, but these effects are likely isolated to aquifers in the eastern third of the basin. In addition, this study illustrates a physical mechanism for groundwater originating in the eastern highlands to recharge aquifers and salars in the western Pampa del Tamarugal Basin over timescales of 10⁴–10⁵ years.