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.     

The mineralogical composition of precursor sediments of calcareous rhythmites: a new approach

Previous studies in Silurian carbonates from Gotland (Sweden) have led to a model for the development of limestone-marl alternations. This model postulates that early diagenesis of precursor sediments without strong primary differences can result in a differentiation by selective dissolution of aragonite in marl beds and reprecipitation of calcite cement in limestone beds. This model is described as a set of mathematical equations that quantify the diagenetic processes (aragonite dissolution and calcite reprecipitation) that occur during the formation of limestone-marl interbeds from a hypothetical homogeneous precursor sediment. The calculations demonstrate that resulting hypothetical limestone-marl alternations show characteristic mathematical relationships between the ratios of the bed thicknesses of limestones and marls on one side, and the carbonate contents, on the other. By reversing this model, the original mineralogical composition of the precursor sediment of real-world rhythmic successions can be determined. In this study, alternations from the Silurian of Gotland, the Cambrian, Devonian, and Mississippian of North America, the Jurassic of France and Germany, and the Cretaceous of France are shown to exhibit mathematical relationships similar to those calculated for hypothetical precursor sediments without primary differences. Therefore, the mineralogical composition of their precursor sediments can be estimated. In contrast, the clear mismatch shown by the Lower Jurassic Belemnite Marls from Dorset indicates that these rhythms did not suffer an early diagenetic overprint. Our model helps to differentiate between rhythmites with strong depositional variations and those without; however, it cannot indicate whether a given alternation is the product of rhythmic diagenesis of a homogeneous precursor sediment or the result of diagenetic enhancement of subtle underlying sedimentary rhythms. For horizontally correlated patterns, such as laterally extensive beds and layers of nodules, an a priori unknown external signal has to be assumed.     

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     

Environmental history of an urban lake: a palaeolimnological study of Lake Jyväsjärvi, Finland

Sedimentary diatom frustules and chironomid remains, in addition to the chemical stratigraphy of 32 elements and organic pollutants such as resin acids, PCB, DDT and its metabolites, were studied from core samples taken from Lake Jyväsjärvi in Central Finland (64° 14 N, 25° 47 E). The sediment profile covered over 200 years, with the oldest samples representing a period of very low human interference. The town of Jyväskylä was established on the lake shore in 1837, and the lake received untreated municipal wastewater from the town up until, 1977. A paper mill started operations in 1872 and began discharging effluent into Lake Jyväsjärvi. In recent years this effluent loading has been reduced. Based on the biological and chemical properties of the sediment strata, five developmental phases were distinguished and named as follows: (1) a pre-industrial phase (approximately up until the 1860s); (2) a phase of early changes in the lake ecosystem (from the 1870s to ca. 1940s); (3) a phase of increasing eutrophication (from ca. 1950 to ca. 1965); (4) a phase of severe pollution (from ca. 1966 to the early-1990s); and (5) a phase of recovery, which proceeded more quickly during the late-1990s following long-term hypolimnetic aeration. It was estimated that the ecological status of the lake changed from good to moderate during the second phase. Due to the poor chemical status of the lake (including increased concentrations of harmful substances) and the pronounced changes in diatom and chironomid communities, the ecological status from 1950 to the early-1990s was classified as bad. The present ecological status, after a slow recovery of about 20 years, can be classified as moderate/poor. Chemical analysis of the sediment revealed that some elements (C, N, P, S, Ba, Cd, Cu, Fe, Pb, Ni and Zn) followed the known history of municipal waste water discharge into the lake, but Hg, Cr and persistent organic pollutants had different stratigraphies, and therefore mainly originated from other sources. Pronounced changes in profundal benthic communities (chironomids) started about 80 years later than those in diatoms, but later changes in chironomid assemblages were greater than those in diatoms.     

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.