Mineralogical and geochemical investigation of clay-rich mine tailings from a closed phosphate mine, Bartow Florida, USA

Clay-rich mine tailings from phosphate mine operations in Florida are a major environmental and economic problem. Options for reclamation and restoration for these tailings are very limited and are fundamentally restricted by poor physical properties such as low mechanical strength, low hydraulic conductivity, and heavy metal content. The major control on these bulk physical properties is the mineralogy of the materials. Eight continuous push borings were obtained to investigate stratigraphy, mineralogy, aspects of geochemistry, and bulk properties of a deposit of clay-rich mine tailings from a phosphate mine near Bartow, Florida that ceased operations in the early 1970s. Stratigraphy is dominated by laminated clay-rich sediment with minor units of silt and sand. An intact kaolinite liner occurs near the impoundment walls and the impoundment floor has approximately 4 m of relief. Moisture content varies from 4.35 to 57.40 wt% and organic content varies from 0.41 to 9.53 wt%. Bulk XRF investigation indicates that the P₂O₅ concentrations vary from approximately 4 to 21 wt%. A very strong correlation (r ² = 0.92) between CaO and P₂O₅ indicates that apatite is a major control on the phosphate. The strong correlation (r ² = 0.77) of Al₂O₃ and TiO₂ suggests that the source materials for this deposit are comparatively uniform. A number of heavy metal elements and trace elements occur. Cr, V, Ni, Cu are interpreted to be in phosphate minerals, largely apatite. Sr and Pb are interpreted to be in both phyllosilicates and phosphate minerals. Two populations of apatite were observed in the clay-sized fraction, one that was Fe and Si- bearing and another that was only Si-bearing. Fe-bearing apatite had Fe₂O₃ contents that varied from 0.38 to 5.32 wt% and SiO₂ contents that varied from 0.90 to 3.32 wt%. The other apatite population had a wider range of SiO₂ contents that varied from 0.77 to 8.80 wt%. TEM imaging shows that apatite grains are dominantly single crystals with lesser amounts of aggregates. Wavellite commonly occurs as individual or clusters of lath-like crystals and the chemical composition differs from the pure aluminium phosphate end member with average concentrations of components being that of CaO (1.57 wt%), Fe₂O₃ (1.98 wt%), SiO₂ (5.94 wt%). In the clay-sized phosphate minerals investigated no fluorine was found above detection limit (approximately 0.15 wt%), nor was any uranium, radium, heavy metal, or REE element detected. The phyllosilicate mineralogy of the deposit is dominated by smectite (montmorillonite with lesser amounts of nontronite), palygorskite, illite and kaolinite. No systematic variation in the relative proportions of phyllosilicates was observed in the clay deposit. Energy dispersive spectroscopy EDS analysis indicates that chemical compositions of phyllosilicates are somewhat typical but overall are enriched with respect to Fe compared to theoretical end members. The relative enrichment of Fe is interpreted to be a primary sedimentary feature. Ca content in smectite minerals is high and may inhibit stabilization using lime or similar methods. The high percentages of montmorillonite and palygorskite explain the high bulk water contents observed. This investigation provides fundamentally new details regarding clay tailing deposits from closed phosphate mines in central Florida which can be used in restoration and reclamation efforts.     

Resuspension of urban soils as a persistent source of lead poisoning in children: A review and new directions

Urban soils act as the repository for a number of environmental burdens, including Pb. Significant attention has been devoted to reducing Pb burdens to children with outstanding success, but the fact that blood Pb levels above 10  μg/dL are disproportionately found in children living in many USA cities (15–20% in some cities compared to a national average of less than 2%) indicates that not all of the sources have been eliminated. Although the health risk of fine particulates has begun to raise concerns in cities, little attention has been paid to Pb associated with these particulates and the potential role of this pathway for continued Pb burdens of urban youth. This review summarizes recent work on particulate resuspension and the role of resuspension of Pb-enriched urban soils as a continued source of bio-available Pb both outside and inside homes, then presents recent efforts to model Pb burdens to children based on the atmospheric parameters that drive particulate resuspension. A strong seasonal relationship is found between atmospheric particulate loading and blood Pb levels in children, and new particulate loading models are presented for a range of US cities involved in the Interagency Monitoring of Protected Visual Environments (IMPROVE) program. These seasonal particulate loading models have implications for a number of respiratory health impacts, but can also be used to calculate seasonal patterns in bio-available Pb redistribution onto contact surfaces (the primary pathway for ingestion-related uptake in toddlers) and assist clinicians in interpreting time-specific blood Pb tests.     

Sources and biological fractionation of Silicon isotopes in the Eastern Equatorial Pacific

Silicon isotopes in dissolved silicic acid were measured in the upper four kilometers between 4°N and 3°S latitude at 110°W longitude in the eastern Equatorial Pacific. Silicon isotopes became progressively heavier with silicic acid depletion of surface water as expected from biological fractionation. The value of ε estimated by applying a steady-state isotope fractionation model to data from all stations between 4°N and 3°S was −0.77 ± 0.12‰ (std. err.). When the analysis was restricted to those stations whose temperature and salinity profiles indicated that they were directly influenced by upwelling of the Equatorial Undercurrent (EUC), the resulting value of ε was −1.08 ± 0.27‰ (std. err.) similar to the value established in culture studies (−1.1‰). When the non steady state Rayleigh model was applied to the same restricted data set the resulting value of ε was significantly more positive, −0.61 ± 0.16‰ (std. err.). To the extent that the equatorial system approximates a steady state these results support a value of −1.1‰ for the fractionation factor for isotopes of Si in the sea. Without the assumption of steady state the value of ε can only be constrained to be between −0.6 and −1.1‰. Silicic acid in Equatorial Pacific Deep Water below 2000 m had a near constant δ³⁰Si of +1.32 ± 0.05‰. That value is significantly more positive than obtained for North Pacific Deep Water at similar depths at stations to the northwest of our study area (0.9-1.0‰) and it is slightly less positive than new measures of the δ³⁰Si of silicic acid from the silicic acid plume centered over the Cascadia basin in the Northeast Pacific (Si(OH)₄ > 180  μM, δ³⁰Si = +1.46 ± 0.12‰ (SD, n = 4). We show that the data from the equator and Cascadia basin fit a general trend of increasing δ³⁰Si(OH)₄ with increasing silicic acid concentration in the deep sea, but that the isotope values from the Northeast Pacific are anomalously light. The observed level of variation in the silicon isotope composition of deep waters from this single ocean basin is considerably larger than that predicted by current models based on fractionation during opal formation with no isotope effect during dissolution. Confirmation of such high variability in deep water δ³⁰Si(OH)₄ within individual ocean basins will require reassessment of the mechanisms controlling the distribution of isotopes of silicon in the sea.     

Petrogenesis of Volcanic Rocks from Saipan and Rota, Mariana Islands, and Implications for the Evolution of Nascent Island Arcs

An ⁴⁰Ar/³⁹Ar age of 45·1 Ma determined for lavas fromnorthern Saipan confirms that these high-silica rhyolites eruptedduring the ‘proto-arc’ stage of volcanism in theIzu–Bonin–Mariana system, which is characterizedelsewhere by eruption of boninitic lavas. Incompatible traceelement concentrations and Sr, Hf, Nd, and Pb isotope ratiosfor these rhyolites are transitional between those of c. 48Ma boninitic lavas and post-38 Ma ‘first-arc’ andesitesand dacites from Saipan and Rota that have typical subduction-relatedcompositions. These transitional compositions are modeled bycrystal fractionation of parental tholeiitic basalt combinedwith assimilation of young boninitic crust. A second stage ofRayleigh fractionation in the upper crust is required by SiO₂concentrations that exceed 77 wt % and near-zero compatibleelement concentrations. First-arc magma compositions are consistentwith fractionation of basalt and assimilation of crust similarin composition to the first-arc magmas themselves. The mantlesources of the proto-arc and first-arc lavas from Saipan andRota are similar to those of Philippine back-arc basin basaltsbased on Nd and Hf isotopic compositions. The Pb isotope compositionsof these lavas are between those of Pacific sea-floor basaltsand Jurassic and younger cherty and clay-rich sediments. Thiscontrasts with the boninitic proto-arc volcanic rocks from Guamand Deep Sea Drilling Project Sites 458 and 459 that have Pbisotope compositions similar to Pacific basin basalts and volcaniclasticsediments. The preferred explanation for the difference in thenature of proto-arc volcanism between Saipan and other fore-arclocations is that the crust ceased extending 3–4 Myr earlierbeneath Saipan. This was caused by a change from mantle upwelling,fore-arc extension, and shallow melting to an environment dominatedby more normal mantle wedge convection, stable crust, and deepermelting. KEY WORDS: rhyolite; andesite; Mariana arc; isotope ratios; trace elements     

Deformation-induced polymorphic transformation: experimental deformation of kyanite, andalusite, and sillimanite

Torsion experiments were performed on the Al₂SiO₅ polymorphs in the sillimanite stability field to determine basic rheological characteristics and the effect of deformation on polymorphic transformation. The experiments resulted in extensive transformation of andalusite and kyanite to sillimanite. No transformation occurred during the hot-press (no deformation) stage of sample preparation, which was carried out at similar P–T conditions and duration as the torsion experiments. Experiments were conducted on fine-grained (< 15 µm) aggregates of natural andalusite, kyanite and sillimanite at 1250 °C, 300 MPa, and a constant shear strain rate of 2 × 10^− 4/s to a maximum shear strain of 400%. Electron back-scattered diffraction (EBSD) analysis of the experiments revealed development of lattice-preferred orientations, with alignment of sillimanite and andalusite [001] slightly oblique to the shear plane. The kyanite experiment could not be analyzed using EBSD because of near complete transformation to sillimanite. Very little strain ( 30%) is required to produce widespread transformation in kyanite and andalusite. Polymorphic transformation in andalusite and kyanite experiments occurred primarily along 500 µm wide shear bands oriented slightly oblique and antithetic to the shear plane and dominated by sub-µm (100–150 nm) fibrolitic sillimanite. Shear bands are observed across the entire strain field preserved in the torsion samples. Scanning transmission electron microscope imaging shows evidence for transformation away from shear bands; e.g. fibrolitic rims on relict andalusite or kyanite. Relict grains typically have an asymmetry that is consistent with shear direction. These experimental results show that sillimanite is by far the weakest of the polymorphs, but no distinction can yet be made on the relative strengths of kyanite and andalusite. These observations also suggest that attaining high bulk strain energy in strong materials such as the Al₂SiO₅ polymorphs is not necessary for triggering transformation. Strain energy is concentrated along grain boundaries, and transformation occurs by a dynamic recrystallization type process. These experiments also illustrate the importance of grain-size sensitive creep at high strains in a system with simultaneous reaction and deformation.     

Annual variations in water storage and precipitation in the Amazon Basin

We combine satellite gravity data from the gravity recovery and climate experiment (GRACE) and precipitation measurements from the National Oceanic and Atmospheric Administration (NOAA) Climate Prediction Center’s (CPC) Merged Analysis of Precipitation (CMAP) and the Tropical Rainfall Measuring Mission (TRMM), over the period from mid-2002 to mid-2006, to investigate the relative importance of sink (runoff and evaporation) and source (precipitation) terms in the hydrological balance of the Amazon Basin. When linear and quadratic terms are removed, the time-series of land water storage variations estimated from GRACE exhibits a dominant annual signal of 250 mm peak-to-peak, which is equivalent to a water volume change of ~1,800 km³. A comparison of this trend with accumulated (i.e., integrated) precipitation shows excellent agreement and no evidence of basin saturation. The agreement indicates that the net runoff and evaporation contributes significantly less than precipitation to the annual hydrological mass balance. Indeed, raw residuals between the de-trended water storage and precipitation anomalies range from ±40 mm. This range is consistent with stream-flow measurements from the region, although the latter are characterized by a stronger annual signal than our residuals, suggesting that runoff and evaporation may act to partially cancel each other.     

Fast error analysis of continuous GPS observations

It has been generally accepted that the noise in continuous GPS observations can be well described by a power-law plus white noise model. Using maximum likelihood estimation (MLE) the numerical values of the noise model can be estimated. Current methods require calculating the data covariance matrix and inverting it, which is a significant computational burden. Analysing 10 years of daily GPS solutions of a single station can take around 2 h on a regular computer such as a PC with an AMD Athlon^TM 64 X2 dual core processor. When one analyses large networks with hundreds of stations or when one analyses hourly instead of daily solutions, the long computation times becomes a problem. In case the signal only contains power-law noise, the MLE computations can be simplified to a process where N is the number of observations. For the general case of power-law plus white noise, we present a modification of the MLE equations that allows us to reduce the number of computations within the algorithm from a cubic to a quadratic function of the number of observations when there are no data gaps. For time-series of three and eight years, this means in practise a reduction factor of around 35 and 84 in computation time without loss of accuracy. In addition, this modification removes the implicit assumption that there is no environment noise before the first observation. Finally, we present an analytical expression for the uncertainty of the estimated trend if the data only contains power-law noise. Electronic supplementary material The online version of this article (doi: ) contains supplementary material, which is available to authorized users.     

Isoprene and Its Oxidation Products Methyl Vinyl Ketone, Methacrolein, and Isoprene Related Peroxides Measured Online over the Tropical Rain Forest of Surinam in March 1998

Airborne measurements of volatile organic compounds (VOC) were performed overthe tropical rainforest in Surinam (0–12 km altitude,2°–7° N, 54°–58° W) using the proton transferreaction mass spectrometry (PTR-MS) technique, which allows online monitoringof compounds like isoprene, its oxidation products methyl vinyl ketone,methacrolein, tentatively identified hydroxy-isoprene-hydroperoxides, andseveral other organic compounds. Isoprene volume mixing ratios (VMR) variedfrom below the detection limit at the highest altitudes to about 7 nmol/molin the planetary boundary layer shortly before sunset. Correlations betweenisoprene and its product compounds were made for different times of day andaltitudes, with the isoprene-hydroperoxides showing the highest correlation.Model calculated mixing ratios of the isoprene oxidation products using adetailed hydrocarbon oxidation mechanism, as well as the intercomparisonmeasurement with air samples collected during the flights in canisters andlater analysed with a GC-FID, showed good agreement with the PTR-MSmeasurements, in particular at the higher mixing ratios.Low OH concentrations in the range of 1–3 × 10⁵molecules cm^-3 averaged over 24 hours were calculated due to lossof OH and HO₂ in the isoprene oxidation chain, thereby stronglyenhancing the lifetime of gases in the forest boundary layer.     

Visibility Analysis with the Multiscale Implicit TIN

Visibility analysis is now a key function of many geographical information systems. It is also one of the most contentious tools, as it is notoriously prone to error. The paper will demonstrate the versatility of the Multiscale Implicit Triangulated Irregular Network (TIN) for the application of intervisibility analysis at multiple resolutions. This approach allows for the integration of three-dimensional (3D) topographic features with the terrain surface. The multiscale TINs are derived from generalising digital contours at a variety of lateral tolerances. The models' performances are evaluated from an extensive field study undertaken in the South Wales valleys. Results suggest that the accuracy of intervisibility analysis is very dependent upon the availability of good quality 3D topographic data. In our study, such data were shown to improve visibility performance by more than 44% over its bare-earth TIN equivalent. Interestingly, generalisation of the TINs had very little effect on visibility performance. In addition, a Monte Carlo approach to sensitivity analysis was found to be detrimental to the accuracy of visibility prediction in the full terrain and topographic models. However, this probable approach can improve intervisibility performance by up to 18% on a bare-earth TIN. The range of these visibility modelling scenarios demonstrate the flexibility of the Multiscale Implicit TIN for digital surface modelling.     

Cross-arc geochemical variations in volcanic fields in Honduras C.A.: progressive changes in source with distance from the volcanic front

A geochemical traverse across Honduras reveals the heterogeneity of the mantle underneath Central America. Alkali basalts from Lake Yojoa (170 km behind the front) have low ⁸⁷Sr/⁸⁶Sr but high La/Yb, and elevated incompatible trace element abundances, consistent with derivation from a normal mid-ocean ridge basalt source mantle via low degrees of melting. These lavas lack evidence for an enriched source thought to be intermingled with normal mid-ocean ridge basalt source mantle beneath most of Central America. The amplitude of the subducted slab signature decreases smoothly with distance from the volcanic front. Lavas from Zacate Grande, the area nearest to the volcanic front (17 km behind the arc), display large ion lithophile element enrichment and high field strength element depletion indicating the involvement of subducted material in magma genesis. Components of subducted material are not evident in lavas from Lake Yojoa, the area furthest from the arc. Basalts and basaltic andesites from Tegucigalpa, 102 km behind the volcanic front, are geochemically intermediate between those of Lake Yojoa and Zacate Grande. The lavas from Tegucigalpa show a decreased influence of the subduction component, and are affected by assimilation-fractional crystallization processes at shallow depths. The gradual decrease in the subducted component from the volcanic front to Zacate Grande, Tegucigalpa and finally Lake Yojoa contrasts with the abrupt decrease documented for southeast Guatemala, the only other area in Central America where a cross-arc transect has been studied. Received: 1 July 1995 / Accepted: 16 July 1997