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     

Present-day oxidative subsidence of organic soils and mitigation in the Sacramento-San Joaquin Delta,California, USA

Subsidence of organic soils in the Sacramento-San Joaquin Delta threatens sustainability of the California (USA) water supply system and agriculture. Land-surface elevation data were collected to assess present-day subsidence rates and evaluate rice as a land use for subsidence mitigation. To depict Delta-wide present-day rates of subsidence, the previously developed SUBCALC model was refined and calibrated using recent data for CO₂ emissions and land-surface elevation changes measured at extensometers. Land-surface elevation change data were evaluated relative to indirect estimates of subsidence and accretion using carbon and nitrogen flux data for rice cultivation. Extensometer and leveling data demonstrate seasonal variations in land-surface elevations associated with groundwater-level fluctuations and inelastic subsidence rates of 0.5–0.8 cm yr^–1. Calibration of the SUBCALC model indicated accuracy of ±0.10 cm yr^–1 where depth to groundwater, soil organic matter content and temperature are known. Regional estimates of subsidence range from <0.3 to >1.8 cm yr^–1. The primary uncertainty is the distribution of soil organic matter content which results in spatial averaging in the mapping of subsidence rates. Analysis of leveling and extensometer data in rice fields resulted in an estimated accretion rate of 0.02–0.8 cm yr^–1. These values generally agreed with indirect estimates based on carbon fluxes and nitrogen mineralization, thus preliminarily demonstrating that rice will stop or greatly reduce subsidence. Areas below elevations of –2 m are candidate areas for implementation of mitigation measures such as rice because there is active subsidence occurring at rates greater than 0.4 cm yr^–1.     

Spatially resolved spectroscopy of the E+A galaxies in the z= 0.32 cluster AC 114

We present spatially resolved intermediate-resolution spectroscopy of a sample of 12 E+A galaxies in the   z = 0.32  rich galaxy cluster AC 114, obtained with the FLAMES multi-integral field unit system on the Very Large Telescope (VLT) of the European Southern Observatory. Previous integrated spectroscopy of all these galaxies by Couch & Sharples had shown them to have strong Balmer line absorption and an absence of [O  ii ]λ3727 emission – the defining characteristics of the 'E+A' spectral signature, indicative of an abrupt halt to a recent episode of quite vigorous star formation. We have used our spectral data to determine the radial variation in the strength of Hδ absorption in these galaxies and hence map out the distribution of this recently formed stellar population. Such information provides important clues as to what physical event might have been responsible for this quite dramatic change in star formation activity in the recent past of these galaxies. We find a diversity of behaviour amongst these galaxies in terms of the radial variation in Hδ absorption: four galaxies show little Hδ absorption across their entire extent; it would appear they were misidentified as E+A galaxies in the earlier integrated spectroscopic studies. The remainder show strong Hδ absorption, with a gradient that is either negative (Hδ equivalent width decreasing with radius), flat or positive . By comparison with numerical simulations we suggest that the first of these different types of radial behaviour provides evidence for a merger/interaction origin, whereas the latter two types of behaviour are more consistent with the truncation of star formation in normal disc galaxies with the Hδ gradient becoming increasingly positive with time after truncation. It would seem therefore that more than one physical mechanism is responsible for E+A formation in the same environment.     

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.     

Sensitive observations of radio recombination lines in Orion and W51: the data and detection of systematic recombination line blueshifts proportional to impact broadening

Sensitive spectral observations made in two frequency bands near 6.0 and 17.6 GHz are described for Orion and W51. Using frequency switching we were able to achieve a dynamic range in excess of 10,000 without fitting sinusoidal or polynomial baselines. This enabled us to detect lines as weak as T _A ∼1 mK in these strong continuum sources. Hydrogen recombination lines with Δn as high as 25 have been detected in Orion. In the Orion data, where the lines are stronger, we have also detected a systematic shift in the line center frequencies proportional to linewidth that cannot be explained by normal optical depth effects.     

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.