Determination of the REE in Geological Reference Materials DTS-1 (Dunite) and PCC-1 (Peridotite) by Ultrasonic and Microconcentric Desolvating Nebulisation ICP-MS

Inductively coupled plasma-mass spectrometry is well suited for the precise, accurate and rapid determination of rare earth elements in most geological samples. However, determination of rare earth elements in certain mantle-derived materials, without applying preconcentration techniques, remains problematical due to low natural concentrations (generally < 1 ng g⁻¹). Consequently, USGS reference materials DTS-1 (a dunite) and PCC-1 (a partially serpentinized harzburgite) have only suggested rather than recommended values for the rare earth elements in reference material compilations. We compared results obtained using two ICP-MS instruments: a U-5000AT ultrasonic nebuliser coupled to a PQ2+ quadrupole ICP-MS and an ELEMENT sector field ICP-MS equipped with a MCN-6000 microconcentric desolvating nebuliser, with the suggested literature values for these two reference materials. Precision and accuracy of analytical methods employed by both instruments were demonstrated by excellent relative standard deviations (< 2%) and inter-laboratory agreement (< 5%) for numerous analyses of BHVO-1 and BIR-1, which are well established with rare earth elements contents at the μg g⁻¹ level. Repeat analyses of DTS-1 and PCC-1 at each laboratory indicate that each method is generally precise to better than 5% at sub-g g⁻¹ levels. Furthermore, values from both instruments generally agree to within 10%. Our DTS-1 and PCC-1 values agree reasonably well with selected data reported in the literature (except for Ce and Sm in DTS-1) but exhibit poorer agreement with reported compilation values. With the demonstrated level of precision and accuracy, we contend that these new values for DTS-1 and PCC-1, generated by two different instruments, are the best estimates of the true whole-rock composition of these samples reported to date.     

Mn-oxides and sequestration of heavy metals in a suburban catchment basin of the Chesapeake Bay watershed

The Chesapeake Bay is greatly impacted by numerous pollutants including heavy metals and understanding the controls on the distribution of heavy metals in the watershed is critical to mitigation and remediation efforts in controlling this type of pollution. Clasts from a stormwater catchment basin draining a subdivision near George Mason University, Fairfax VA (38°50.090°N 78°19.204°W) were investigated using X-ray diffraction (XRD), Scanning electron microcopy (SEM) and energy dispersive spectroscopy (EDS) to determine the nature of Mn-oxide coatings and relationship to bound heavy metals. Mn-oxides are poorly crystalline and occur as subhedral to anhedral platy particles and more rarely as euhedral plates. Micronodules are a commonly observed texture. Chemical compositions of coatings are variable with average major constituent concentrations being Mn (33.38 wt%), Fe (11.88 wt%), Si (7.33 wt%), Al (5.03 wt%), and Ba (0.90 wt%). Heavy metals are found in the coatings with Zn being most prevalent, occurring in approximately 58% of analyses with an average concentration of (0.66 wt%). Minor amounts of Co, Ni, Pb, and Cl are observed. Heavy metals and Cl are interpreted as being derived from road pollution. Mn-oxides can serve as a sequestration mechanism for pollution but may also release heavy metals. Field and laboratory observations indicate Mn-oxides occurring on the surface of the clasts can be mechanically mobilized. This is a mechanism for transporting heavy metals into the Chesapeake Bay watershed. Deicing agents may serve as a mechanism to release heavy metals through cation exchange and increased ionic strength. This is the first detailed mineralogical investigation of Mn-oxides and the roles they may play in pollution in the Chesapeake Bay.     

Community‐Derived Standards for LA‐ICP‐MS U‐(Th‐)Pb Geochronology – Uncertainty Propagation,Age Interpretation and Data Reporting

The LA‐ICP‐MS U‐(Th‐)Pb geochronology international community has defined new standards for the determination of U‐(Th‐)Pb ages. A new workflow defines the appropriate propagation of uncertainties for these data, identifying random and systematic components. Only data with uncertainties relating to random error should be used in weighted mean calculations of population ages; uncertainty components for systematic errors are propagated after this stage, preventing their erroneous reduction. Following this improved uncertainty propagation protocol, data can be compared at different uncertainty levels to better resolve age differences. New reference values for commonly used zircon, monazite and titanite reference materials are defined (based on ID‐TIMS) after removing corrections for common lead and the effects of excess ²³⁰Th. These values more accurately reflect the material sampled during the determination of calibration factors by LA‐ICP‐MS analysis. Recommendations are made to graphically represent data only with uncertainty ellipses at 2s and to submit or cite validation data with sample data when submitting data for publication. New data‐reporting standards are defined to help improve the peer‐review process. With these improvements, LA‐ICP‐MS U‐(Th‐)Pb data can be considered more robust, accurate, better documented and quantified, directly contributing to their improved scientific interpretation.     

The influence of edge sites on the development of surface charge on goethite nanoparticles: A molecular dynamics investigation

Large-scale molecular simulation of proton accumulations were carried out on (i) (110) and (021) slabs immersed in aqueous solution and (ii) a series of model goethite nanoparticles of dimension 2 to 8 nm with systematically varying acicularity and (110)/(021) surface areas. In the slab systems, the (021) surface exhibits 15% more proton charge per unit area than the (110) surface. In the particulate systems, the acicular particles having the highest (110)/(021) ratio accumulate the most charge, opposite to the trend expected from the slab simulations, indicating that, at length scales on the order of 10 nm, the slab results are not a good indicator of the overall charging behavior of the particles. The primary reason for the discrepancy between the particulate systems and slab systems is the preferential accumulation of protons at acute (110)-(110) intersections. Charge accumulates preferentially in this region because excess proton charge at an asperity is more effectively solvated than at a flat interface.     

Assessment of Submarine Groundwater Discharge (SGD) as a Source of Dissolved Radium and Nutrients to Moorea (French Polynesia) Coastal Waters

Previous work has documented large fluxes of freshwater and nutrients from submarine groundwater discharge (SGD) into the coastal waters of a few volcanic oceanic islands. However, on the majority of such islands, including Moorea (French Polynesia), SGD has not been studied. In this study, we used radium (Ra) isotopes and salinity to investigate SGD and associated nutrient inputs at five coastal sites and Paopao Bay on the north shore of Moorea. Ra activities were highest in coastal groundwater, intermediate in coastal ocean surface water, and lowest in offshore surface water, indicating that high-Ra groundwater was discharging into the coastal ocean. On average, groundwater nitrate and nitrite (N + N), phosphate, ammonium, and silica concentrations were 12, 21, 29, and 33 times greater, respectively, than those in coastal ocean surface water, suggesting that groundwater discharge could be an important source of nutrients to the coastal ocean. Ra and salinity mass balances indicated that most or all SGD at these sites was saline and likely originated from a deeper, unsampled layer of Ra-enriched recirculated seawater. This high-salinity SGD may be less affected by terrestrial nutrient sources, such as fertilizer, sewage, and animal waste, compared to meteoric groundwater; however, nutrient-salinity trends indicate it may still have much higher concentrations of nitrate and phosphate than coastal receiving waters. Coastal ocean nutrient concentrations were virtually identical to those measured offshore, suggesting that nutrient subsidies from SGD are efficiently utilized.     

QUEST on DASI: a South Pole CMB polarization experiment

QUEST on DASI is a ground-based, high-sensitivity, high-resolution (ℓ_max2500) experiment designed to map CMB polarization at 100 and 150 GHz and to measure the power spectra from E-modes, B-modes from lensing of the CMB, and B-modes from primordial gravitational waves. The experiment comprises a 2.6 m Cassegrain optical system, equipped with an array of 62 polarization-sensitive bolometers (PSBs), located at the South Pole. The instrument is designed to minimize systematic effects; features include differencing of pairs of orthogonal PSBs within a single feed, a rotatable achromatic waveplate, and axisymmetric rotatable optics. In addition the South Pole location allows both repeatable and highly controlled observations. QUEST on DASI will commence operation in early 2005.     

Nd isotopic evidence for the position of southernmost Indian terranes within East Gondwana

Sm-Nd model ages of orthopyroxene-bearing massif charnockites from the Cardamom Hills Massif and adjoining supracrustal rocks from the Kerala Khondalite Belt in southernmost India are used to infer some of the relationships within these rocks and between them and neighboring areas. Most of these rocks have model ages of 2.1–2.8 Ga with most charnockites in the range 2.2–2.6 Ga. Thus, 3.0–3.4 Ga Archean rocks to their north did not contribute material to either suite and the two suites may have been juxtaposed after formation of the supracrustal rocks. The similarity of Sm-Nd isotope systems in the two units studied here supports an argument that the massif charnockites were the primary sole source of the detritus incorporated into the supracrustal rocks. A cordierite gneiss, representative of a relatively minor lithology in the supracrustal belt, has a model age of 1.3 Ga. The protolith of this gneiss not only formed from much younger material than the rest of the belt but also formed significantly after the other metasedimentary rocks. The source material of the gneiss protolith may have been located in the Wanni and Vijayan Complexes of Sri Lanka. The overlap of the model ages of rocks in this area and those in the Highland Complex of Sri Lanka supports the notion that these two sets of rocks were joined to each other in Gondwana. They belong to a belt that ran from Antarctica through Sri Lanka and India into Madagascar. This belt was involved in Pan-African tectono-metamorphism, as reflected in the 550 Ma age of the last, granulite-forming, event throughout the belt.     

Assessing selected natural and anthropogenic impacts on freshwater lens morphology on small barrier Islands: Dog Island and St. George Island, Florida, USA

Abstract The freshwater lens morphologies of the barrier islands Dog Island and St. George Island on the panhandle coast of Florida (FL), USA, are controlled to varying degrees by both natural and anthropogenic factors. Variable-density groundwater flow models confirm that spatial variability of recharge values can account for the observed lens asymmetry on these islands. The depth to the base of the lens does not vary significantly seasonally. Human development has altered recharge patterns in some areas, locally thinning the freshwater lens. Aqueduct water supply to St. George Island represents 7–25% of natural recharge; higher recharge rates are required to simulate the lens on St. George Island than on Dog Island. On both islands, coastal erosion rates are sufficiently rapid that the freshwater lens may not be in equilibrium with current boundary conditions.

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Resumen Las morfologías de los lentes de agua dulce en las islas de barrera: Islas Dog y St. George, en la costa alargada y estrecha de Florida, EUA, están controladas en diferentes grados por factores antropogénicos y naturales. Los modelos de flujo con densidad variable del agua subterránea, confirman que la variabilidad espacial de los valores de recarga, pueden ser la causa de la asimetría observada en los lentes de estas islas. La profundidad hasta la base de los lentes no varía significativamente con las estaciones climáticas. El desarrollo humano ha alterado las tendencias de recarga en algunas áreas, causando adelgazamiento local de los lentes de agua dulce. El abastecimiento de agua del acueducto en la Isla St. George, representa entre 7% y 25% de la recarga natural; por otro lado se necesitan cantidades mayores de recarga para simular los lentes en la Isla St. George que en la Isla Dog. En ambas islas, las tasas de erosión costera son tan rápidas, que las lentes de agua dulce podrían no estar en equilibrio con las condiciones actuales de frontera.

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Résumé La morphologie des lentilles deau douce des îles de Dog et de St. George, situés dans le district côtier de Florida-Etats Unis est contrôlé dans une mesure variable par des facteurs naturelles et humaines. Les modèles découlement à densité variable des eaux souterraines confirment que la variation spatiale de la recharge peut expliquer les asymétries observées des lentilles des cettes îles. La profondeur des lentilles ne présente pas des variations saisonnières importantes. Les activités humaines ont modifié la recharge dans certaines zones en amincissant localement les lentilles deau douce. Lalimentation en eaux de lîle de St. George représente 7–25% de la recharge naturelle; pour simuler les lentilles de lîle de Dog il a été nécessaire dintroduire des valeurs plus élevées de la recharge par rapport aux ceux utilisés pour lîle de St. George. Pour les deux îles lérosion côtière est assez rapide ainsi que les lentilles de eau douce ne sont pas en équilibre avec les conditions à la frontière.