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.     

CLIMAP SSTs re-revisited

Since the 1976 publication of the CLIMAP ice age sea surface temperature (SST) reconstruction showing a 1–2 ^∘C tropical cooling a substantial debate has arisen as to whether tropical SSTs may instead have been 4–5^∘ colder than present. Herein I review the arguments for large SST variations and question a number of key findings, particularly the validity of ice-age coral SST estimates and “down-projecting” tropical snowline changes to the surface. GCM results indicate that an intermediate solution requiring ∼2.5 ^∘C warm pool cooling is consistent with most quantitative low elevation surface land data and is small enough to allow the persistence of tropical biota in the ocean during glacial times. The proposal reduces estimated ice-age climate sensitivity (for a doubling of CO₂) from a “high-end” sensitivity of about 4.5 ^∘C (for a 5–6 ^∘C tropical cooling) to a “mid-range” sensitivity of about 3.0 ^∘C for a 2.5 ^∘C warm-pool decrease. Received: 28 July 1999 /Accepted: 12 August 1999     

Phytoplankton diversity and chlorophyll-A in a polluted estuary

The quantity of phytoplankton in Newark Bay, New Jersey as indicated by chlorophyll-a content of the water, is low in the winter and early spring, and fluctuates greatly during the spring and summer. Chlorophyll-a concentrations are generally less than 20 μg/l until April. Between April and August, three phytoplankton blooms were indicated by chlorophyll-a concentrations as high as 81.4 μg/l. Net phytoplankton diversity values indicated generally eutrophic conditions; however, there was no significant correlation between diversity and chlorophyll-a concentrations. A role of nannoplankton in blooms is indicated.     

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.     

The solubility of quartz in aqueous sodium chloride solution at 350°C and 180 to 500 bars

The solubility of quartz in 2, 3, and 4 molal NaCl was measured at 350°C and pressures ranging from 180 to 500 bars. The molal solubility in each of the salt solutions is greater than that in pure water throughout the measured pressure range, with the ratio of solubility in NaCl solution to solubility in pure water decreasing as pressure is increased. The measured solubilities are significantly higher than solubilities calculated using a simple model in which the water activity in NaCl solutions decreases either in proportion to decreasing vapor pressure of the solution as salinity is increased or in proportion to decreasing mole fraction of water in the solvent.     

MELTWATER FLUXES AT AN ARCTIC FOREST-TUNDRA SITE

Models of surface energy balance and snow metamorphism are utilized to predict the energy and meltwater fluxes at an Arctic site in the forest–tundra transition zone of north-western Canada. The surface energy balance during the melt period is modelled using an hourly bulk aerodynamic approach. Once a snowcover becomes patchy, advection from the bare patches to the snow-covered areas results in a large spatial variation in basin snowmelt. In order to illustrate the importance of small-scale, horizontal advection, a simple parameterization scheme using sensible heat fluxes from snow free areas was tested. This scheme estimates the maximum horizontal advection of sensible heat from the bare patches to the snow-covered areas. Calculated melt was routed through the measured snowcover in each landscape type using a variable flow path, meltwater percolation model. This allowed the determination of the spatial variability in the timing and magnitude of meltwater release for runoff. Model results indicate that the initial release of meltwater first occurred on the shallow upland tundra sites, but meltwater release did not occur until nearly two weeks later on the deep drift snowcovers. During these early periods of melt, not all meltwater is available for runoff. Instead, there is a period when some snowpacks are only partially contributing to runoff, and the spatial variation of runoff contribution corresponds to landscape type. Comparisons of melt with and without advection suggests that advection is an important process controlling the timing of basin snowmelt.     

Sources of dissolved REE in mountainous streams draining granitic rocks, Sierras Pampeanas (Córdoba, Argentina)

Stream waters draining granitic terrains from the highest part (850 to 2200 m a.s.l.) of Sierras Pampeanas (Córdoba, Argentina, ∼32°S, ∼65°W) were sampled in order to define sources and distribution of dissolved rare earth elements (REE), and to describe the geochemical processes that govern their mobility. The contribution of the regional granite to the dissolved REE pool in stream water is limited due to the physical conditions predominating in the area (i.e., steep slopes and semiarid climate). Therefore, precipitation is considered a seasonally significant source controlling REE concentration in stream water. Dissolved REE concentrations are inversely correlated with monthly precipitation and rainfall frequency. During the rainy season (i.e., the austral summer) REE concentrations in stream water are lower than during the dry season (i.e., austral winter). Such low concentrations reflect the balance between the REE input from precipitation and their removal by adsorption. In contrast, during the dry season, the longer residence time of water within fractures and colluvium determines an increased REE concentration in the base flow. Lower pH values also contribute to raise REE concentration through desorption from mineral surfaces.     

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.