Copper(II) humate mobility in kaolinite soil

An investigation of the influence of humate on the mobility of copper(II) ions in a kaolinite soil using leaching tests and electrokinetic experiments is reported. The data are interpreted in terms of humate–copper–clay interactions and humate electrical charge. Humate is mostly immobile below pH8 but is more mobile in alkaline conditions (sorption to kaolinite reduces its mobility in neutral conditions). Copper humate complexes are mobile in both acidic and alkaline conditions, but not in neutral conditions where they are sorbed. The dissolved copper humate complexes that form in acidic conditions are positively charged. The net effect of humate is to increase cupric ion mobility in kaolinite soil, especially in alkaline conditions.     

Reconstruction of palaeosalinity using carbon isotopes and benthic associations: a comparison

Carbon and oxygen isotopes were determined on 40 recrystallized shells of Late Jurassic bivalves from the Lusitanian Basin of Portugal. In contrast with the oxygen isotopes, which exhibited considerable diagenetic distortion, the carbon isotopes are thought to preserve a record of the salinity of the Jurassic marginal marine seas in which these bivalves lived. The reconstructed palaeosalinities range from 35%o (euhaline) to 5% (oligohaline). Comparing these values with the palaeosalinity reconstructed from a palaeoecological analysis of 17 stratigraphic levels within the basin, the independently derived values agree in most cases. Strongly differing values are explained as being due to biotic factors and to diagenetic distortion of the isotopic signal; they are less likely to be due to smallscale time-averaging or insufficient microstratigraphic sampling. On the whole, the carbon isotope analyses are thought to produce reasonable palaeosalinity values, although data from infaunal, originally aragonitic bivalves appear to be less reliable than those from epifaunal bivalves with a predominantly or exclusively calcitic shell. As diagenetic alteration of the carbon isotope signal is, however, unpredictable and biotic effects on the isotopic composition are insufficiently known, palaeosalinity reconstructions based on stable isotope data should be supported by palaeoecological data.     

Improved Petrological Modal Analyses from X-ray Powder Diffraction Data by use of the Rietveld Method I. Selected Igneous, Volcanic, and Metamorphic Rocks

Mineral modes have been determined for specimens of eight rocktypes from CuK X-ray powder diffraction data using the Rietveldmethod. The samples include two granites, a granodiorite, adamellite,gabbro, basalt, trachyte, and two granulite-facies metamorphicrocks. Up to eight individual mineral components have been measuredin each sample (no glassy phases were observed), with a detectionlimit of {small tilde}1 wt.%, depending on the mineral assemblage.Marked variations in grain size (i.e., granite vs. trachyte)provide no difficulties for the X-ray method. The X-ray resultscompare very favourably with (1) optical modes determined forthe medium–coarse-grained samples by point counting, (2)normative calculations obtained using locally enhanced catanormand mesonorm software, and (3) corresponding Rietveld modesdetermined, for two samples, from neutron powder data. Wheredifferences occur, these are discussed in relation to the limitationsof each of the methods. The improved accuracy of the X-ray method is due primarily tothe incorporation of the full diffraction profile in the Rietveldanalysis calculations, and the elimination of preferred orientationby collecting the data from samples packed in glass capillaries(i.e., Debye–Scherrer mode). The good agreement of theX-ray and neutron modes shows that the usual problems encounteredwith microabsorption, extinction, and sampling are of littleconcern in these rocks. The results highlight one of the majoradvantages provided by Rietveld modal analysis over the moretraditional ‘reference intensity’ X-ray methods,namely, that the crystal chemistry (and thus the calibrationconstants) of the individual phases can be adjusted dynamicallyduring each individual analysis. This not only provides moreaccurate phase abundances, but also gives important supplementaryinformation about the mineralogy of the major components.     

Analysis of mutations in the p53 tumor suppressor gene and Ki- and Ha-ras proto-oncogenes in hepatic tumors of European flounder (Platichthys flesus).

DNA from five tumors, three other-injured livers and two normal liver tissue samples from the European flounder were analyzed for mutations in exons 5-8 of the tumor suppressor gene p53 and at codons 12, 13 and 61 of Ha- and Ki-ras proto-oncogenes. No tumor-specific mutations were identified by direct sequencing and single-strand conformation polymorphism of these genes. A number of silent polymorphisms were noted in p53. In addition to a need for more extensive analyses of flounder liver tumor samples for ras or p53 mutations, other cancer-related genes should be investigated.     

Improved Resolution of Ambient Flow through Fractured Rock with Temperature Logs

In contaminant hydrogeology, investigations at fractured rock sites are typically undertaken to improve understanding of the fracture networks and associated groundwater flow that govern past and/or future contaminant transport. Conventional hydrogeologic, geophysical, and hydrophysical techniques used to develop a conceptual model are often implemented in open boreholes under conditions of cross-connected flow. A new approach using high-resolution temperature (±0.001°C) profiles measured within static water columns of boreholes sealed using continuous, water-inflated, flexible liners (FLUTe™) identifies hydraulically active fractures under ambient (natural) groundwater flow conditions. The value of this approach is assessed by comparisons of temperature profiles from holes (100 to 200 m deep) with and without liners at four contaminated sites with distinctly different hydrogeologic conditions. The results from the lined holes consistently show many more hydraulically active fractures than the open-hole profiles, in which the influence of vertical flow through the borehole between a few fractures masks important intermediary flow zones. Temperature measurements in temporarily sealed boreholes not only improve the sensitivity and accuracy of identifying hydraulically active fractures under ambient conditions but also offer new insights regarding previously unresolvable flow distributions in fractured rock systems, while leaving the borehole available for other forms of testing and monitoring device installation.     

Sea-level rise impacts on longitudinal salinity for a low-gradient estuarine system

Climatic Change - Salinity response to sea-level rise is evaluated for a low-gradient, tidally active estuary, the lower St. Johns River, Florida. A high-resolution numerical model is forced by...     

Alteration processes in the CV chondrite parent body based on analysis of NWA 2086 meteorite

Analysis of the NWA 2086 CV3 chondrite showed a matrix/chondrule ratio of 52%, similar to Bali, Mokoia, and Grosanaja. Nearly twice as many chondrule fragments as intact ones demonstrate that an early fragmentation phase occurred prior to final accretion. After this event, no substantial mechanical change or redeposition is evident. Rims with double‐layered structures were identified around some chondrules, which, in at least one case, is attributed to an accretionary origin. The rim's outer parts with a diffuse appearance were formed by in situ chemical alteration. During this later process, Mg content decreased, Fe content increased, and olivine composition was homogenized, producing a rim composition close to that of the matrix. This alteration occasionally happened along fractures and at confined locations, and was probably produced by fluid interactions. Iron oxides are the best candidate for a small grain‐sized alteration product; however, technical limitations in the available equipment did not allow exact phase identification. These results suggest that NWA 2086 came from a location (possible more deeply buried) in the CV parent body than Mokoia or Bali, and suffered less impact effects—although there is no evidence of sustained thermal alteration. This meteorite may represent a sample of the CV parent asteroid interior and provide a useful basis for comparison with other CV meteorites in the future.     

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