The use of acidimetric titration as a novel approach to study particulate trace metal speciation and mobility: Application to sediments of the Scheldt estuary

The study of trace metal speciation has benefited from a great deal of interest leading to the development and the diversification of sequential extraction schemes (SES), which triggered the need for harmonization by the standard, measurements and testing programme (SM & T). However, some uncertainties still persist in the application of the harmonized 3-step protocol, because of the difficulty in conceptualizing a technique that can be applied to environmental samples irrespective of their nature. The alternative method proposed in this study is based on the solubility of the sample components progressively dissolved during the course of an acidimetric titration by 1 mol L⁻¹ HCl. The major HCl-reactive mineralogical components are identified using mass balance calculation of H⁺ consumed by their dissolution together with the amount of major elements released into solution. The speciation of minor and trace elements is investigated by comparing their titrations to those of the major elements. This approach is much simpler than SES because it uses simple non-selective H⁺ at room temperature instead of a complex experimental design of so-called specific reagents. The different mineral components of the solid are no longer operationally defined and the problem of selectivity is irrelevant to the titration approach. The method was applied to several sediment samples from the Scheldt estuary and the particulate phase was further examined by Scanning Electron Microprobe and X-ray Diffraction techniques. The nearly complete consumption of H⁺ in the suspension is balanced by the total dissolution of carbonates and Fe-oxyhydroxides. In contrast to the speciation inferred from the Tessier SES, the acidimetric titration has demonstrated that the carbonate phase does not significantly contain trace metals with the exceptions of 40% of the Mn and 30% of the Co. In contrast, the Fe-oxyhydroxides seem to play a major role and account for 70% of Pb and 20% of Cr, in addition to 60% of P and additional amounts of 20% Co and 40% Mn. 70% of the Cu also occur in the oxyhydroxide phase, more likely coprecipitated with gibbsite. 90% of the Cd and 85% of Zn can be attributed to the Acid Volatile Sulfide (AVS) phase as evidenced from S titration. The acidimetric titration method not only provides information on the speciation of trace metals but also allows the quantification of their reactivity and mobility, if one considers that the titration roughly mimics pH changes that may occur as a result of chemical disequilibrium in the environment. The results demonstrate the potential of the acidimetric titration as an alternative to SES protocols in geochemical and environmental regulation studies. This method is applicable to a wide variety of environmental materials with little or minor adjustments.     

Chemical signature of intermediate water masses along western Portuguese margin

Although the circulation of intermediate water masses in the eastern North Atlantic remains poorly defined, the presence of fresher intermediate waters, the Sub-Artic (SAIW) and the Antarctic Intermediate Water (AAIW), as well the saline intermediate Mediterranean Water (MW), has been tracked using biogeochemical properties. Here we assess the hydrographic and chemical structures of intermediate waters along the western Portuguese margin by examining the vertical distributions and property-property plots of chemical tracers (oxygen and nutrients). AAIW was traced by low oxygen and high nutrients, while SAIW was recognized by low nutrients. The Mediterranean Water (MW) undercurrent is shown to spread towards the eastern flank of Gorringe bank. Concurrently, the fresher waters gained salt by direct incorporation of MW, while this water was enriched in nutrients on its way northward and westward owing, to a great extent, to the entrainment of an AAIW branch. The distributions of nutrients and apparent oxygen utilization are discussed in terms of regional ocean circulation. Our analysis suggests a circulation pattern of the various intermediate waters along the western Portuguese margin: MW extends all over the area, but its presence is more pronounced around cape St. Vincent; SAIW apparently moves southward, reaching the Gorringe bank region, and AAIW flows northward along the coast and around the bank.     

Impact of Earth radiation pressure on GPS position estimates

GPS satellite orbits available from the International GNSS Service (IGS) show a consistent radial bias of up to several cm and a particular pattern in the Satellite Laser Ranging (SLR) residuals, which are suggested to be related to radiation pressure mismodeling. In addition, orbit-related frequencies were identified in geodetic time series such as apparent geocenter motion and station displacements derived from GPS tracking data. A potential solution to these discrepancies is the inclusion of Earth radiation pressure (visible and infrared) modeling in the orbit determination process. This is currently not yet considered by all analysis centers contributing to the IGS final orbits. The acceleration, accounting for Earth radiation and satellite models, is introduced in this paper in the computation of a global GPS network (around 200 IGS sites) adopting the analysis strategies from the Center for Orbit Determination in Europe (CODE). Two solutions covering 9 years (2000–2008) with and without Earth radiation pressure were computed and form the basis for this study. In previous studies, it has been shown that Earth radiation pressure has a non-negligible effect on the GPS orbits, mainly in the radial component. In this paper, the effect on the along-track and cross-track components is studied in more detail. Also in this paper, it is shown that Earth radiation pressure leads to a change in the estimates of GPS ground station positions, which is systematic over large regions of the Earth. This observed “deformation” of the Earth is towards North–South and with large scale patterns that repeat six times per GPS draconitic year (350 days), reaching a magnitude of up to 1 mm. The impact of Earth radiation pressure on the geocenter and length of day estimates was also investigated, but the effect is found to be less significant as compared to the orbits and position estimates.     

E (B-V) determination from an UV-visual two-colour diagram: O and B stars in the catalogue of stellar ultraviolet fluxes

We present here, for the O and B type stars in the Catalogue of Stellar Ultraviolet Fluxes, an approach which does not require a precise knowledge of spectral type and luminosity class for derivingE(B-V) colour excesses. The method is based on the use of an UV-visual two-colour diagram; galactic variations in the interstellar extinction law are analyzed and fully taken into account. Our results have been compared with those derived by using the differences between observed and intrinsic colours for stars with known spectral classification. The very good agreement in a large number of cases (94 per cent) demonstrates that our approach permits the derivation of reliable colour excess values for early type stars even if only a rough spectral classification is available.     

Impacts of primary deforestation upon limestone slopes in northern Vancouver Island, British Columbia

Effects of deforestation upon slopes in limestones and in volcanic rocks in the Benson River valley, northern Vancouver Island, have been investigated quantitatively. Postlogging soil erosion and vegetal regeneration success were assessed by measuring soil depth, percent bare rock and moss cover, and the numbers and diversity of trees, shrubs, and plants on 25 sampling sites, each containing ten measuring quadrats selected at random. Sixteen sites were on the Quatsino Formation, a well-karstified limestone, and nine on the Karmutsen Formation of basaltic lavas. Eight sites were of virgin forest, 16 were logged between 1970 and 1983, and one (on limestone) was logged in 1911. Both bedrock types were significantly affected by the cutting. There was greater loss of soil and an increase in bare rock on the limestones. Erosion was increased significantly by burning on the limestones but not on the volcanics. Within-group comparisons on the limestones determined that steeper slopes and harder burned areas suffered the most and are slowest to regenerate. Volume of timber on the 1911 site was 19 percent of that in similar uncut forest sites. It appears that complete recovery on the barren limestone slopes will require at least some centuries.     

On the Occurrence of Zellia from the Maping Limestone of Chengkung, Central Yunnan

INTRODUCTIONThe specimens described in the present paper were collected in 1939 by the late Mr. T. Y. Hsu and Mr. C. S. Pien from the Maping limestone exposed E of Tuikoshan, Chengkung district, Central Yunnan. All specimens belong to Zellia, a subgenus of Pseudoschwagerina; three forms may be referred to known subspecies while two are new.     

The development of three-dimensional current system during a magnetospheric substorm

It is suggested that the pattern of three-dimensional substorm current circuit varies significantly even during the lifetime of a single substorm. This gives rise to quite complex time variations of the magnetic field at low latitude stations even for relatively isolated substorms. To verify this, three-dimensional current models with time dependent spatial variations are used to simulate one type of complex low-latitude “substorm signature”. It is shown that the utmost care should be exercised in determining different substorm phases on the basis of such a signature. The results indicate also that, in certain longitudes in the evening sector, one should expect distinct differences in characteristics between positive bays observed on the ground and at the synchronous distance.     

Zircon and whole-rock Nd-Pb isotopic provenance of Middle and Upper Ordovician siliciclastic rocks, Argentine Precordillera

Graptolite‐bearing Middle and Upper Ordovician siliciclastic facies of the Argentine Precordillera fold‐thrust belt record the disintegration of a long‐lived Cambro‐Mid Ordovician carbonate platform into a series of tectonically partitioned basins. A combination of stratigraphic, petrographic, U‐Pb detrital zircon, and Nd‐Pb whole‐rock isotopic data provide evidence for a variety of clastic sediment sources. Four Upper Ordovician quartzo‐lithic sandstones collected in the eastern and central Precordillera yield complex U‐Pb zircon age spectra dominated by 1·05–1·10 Ga zircons, secondary populations of 1·22, 1·30, and 1·46 Ga, rare 2·2 and 1·8 Ga zircons, and a minor population (<2%) of concordant zircons in the 600–700 Ma range. Archaean‐age grains comprise <1% of all zircons analysed from these rocks. In contrast, a feldspathic arenite from the Middle Ordovician Estancia San Isidro Formation of the central Precordillera has two well‐defined peaks at 1·41 and 1·43 Ga, with no grains in the 600–1200 Ma range and none older than 1·70 Ga. The zircon age spectrum in this unit is similar to that of a Middle Cambrian quartz arenite from the La Laja Formation, suggesting that local basement rocks were a regional source of ca 1·4 Ga detrital zircons in the Precordillera Terrane from the Cambrian onwards. The lack of grains younger than 600 Ma in Upper Ordovician units reinforces petrographic data indicating that Ordovician volcanic arc sources did not supply significant material directly to these sedimentary basins. Nd isotopic data (n = 32) for Middle and Upper Ordovician graptolitic shales from six localities define a poorly mixed signal [ɛ_Nd(450 Ma) = −9·6 to −4·5] that becomes more regionally homogenized in Upper Ordovician rocks (−6·2 ± 1·0; T_DM = 1·51 ± 0·15 Ga; n = 17), a trend reinforced by the U‐Pb detrital zircon data. It is concluded that proximal, recycled orogenic sources dominated the siliciclastic sediment supply for these basins, consistent with rapid unroofing of the Precordillera Terrane platform succession and basement starting in Mid Ordovician time. Common Pb data for Middle and Upper Ordovician shales from the western and eastern Precordillera (n = 15) provide evidence for a minor (<30%) component that was likely derived from a high‐μ (U/Pb) terrane.     

Large-scale cold water dispersant effectiveness experiments with Alaskan crude oils and Corexit 9500 and 9527 dispersants

There continues to be reluctance in some jurisdictions to use chemical dispersants as a viable countermeasure for accidental oil spills. One argument used by some opponents to dispersant use is that “chemical dispersants do not work effectively in cold water”. To address this issue, the U.S. Minerals Management Service (MMS) funded and conducted two series of large-scale dispersant experiments in very cold water at Ohmsett - The National Oil Spill Response Test Facility, located in Leonardo, New Jersey in February-March 2006 and January-March 2007. Alaska North Slope, Endicott, Northstar and Pt. McIntyre crude oils and Corexit 9500 and Corexit 9527 dispersants were used in the two test series. The crude oils were tested both when fresh and after weathering. Results demonstrated that both Corexit 9500 and Corexit 9527 dispersants were 85-99% effective in dispersing the fresh and weathered crude oils tested at cold temperatures. The MMS expects that results from these test series will assist government regulators and responders in making science based decisions on the use of dispersants as a response tool for oil spills in the Arctic.