The ionic strength dependence of lead (II) carbonate complexation in perchlorate media

Lead speciation in many aqueous geochemical systems is dominated by carbonate complexation. However, direct observations of Pb²⁺ complexation by carbonate ions are few in number. This work represents the first investigation of the equilibrium over a range of ionic strength. Through spectrophotometric observations of formation at 25 °C in NaHCO₃-NaClO₄ solutions, formation constants of the form were determined between 0.001 and 5.0 molal ionic strength. Formation constant results were well represented by the equation:

     

Absorption and fluorescence properties of rainwater during the cold season at a town in Western Portugal

This study aims at evaluating the variability of the optical properties of chromophoric dissolved organic matter (CDOM) of rainwater during the cold season, specifically between Autumn and Winter periods. The spectroscopic characteristics of rainwater samples collected at a town (Aveiro) in western Portugal were assessed by UV-Vis absorbance and three-dimensional excitation-emission matrix (EEM) fluorescence spectroscopies. Rainwater samples showed similar characteristics to those of natural humic substances when analysed by UV-Vis absorbance spectroscopy, but a significant difference was observed in the volume weight average (VWA) of absorbances between Autumn and Winter. In general, the EEM fluorescence spectra of the Autumn and Winter samples disclosed the presence of six fluorophores with different VWA specific fluorescence intensities: three humic-like (λ _excitation/λ _emission ≈ 230/415 nm; 290/415 nm; and 340/415 nm) and three protein-like (λ _excitation/λ _emission ≈ 230/350 nm; 280/340 nm; and 225/300 nm), but one of the humic-like peaks (≈340/415 nm) does not always appear in the EEM fluorescence spectra of the Winter samples. During the cold season, chromophoric compounds are important constituents of rainwater dissolved organic matter and the presence of these highly absorbing and fluorescing compounds may exert a determining effect in atmospheric absorption of solar radiation.     

Strike-slip tectonics within the SW Baltic Sea and its relationship to the inversion of the Mid-Polish Trough—evidence from high-resolution seismic data

The SW Baltic Sea occupies an area where crustal-scale regional tectonic zones of different age merge and overlap, creating a complex tectonic pattern. This pattern influenced the evolution of the Mesozoic sedimentary basin in this area. We present an interpretation of new high-resolution seismic data from the SW Baltic Sea which provided new information both on modes of the Late Cretaceous inversion of this part of the Danish–Polish Mesozoic basin system as well as on relationship between tectonic processes and syn-tectonic depositional systems. Within the Bornholm–Dar owo Fault Zone, located between the Koszalin Fault and Christiansø Block, both strike-slip and reverse faulting took place during the inversion-related activity. The faulting was related to reactivation of extensional pre-Permian fault system. Syn-tectonic sedimentary features include a prominent, generally S- and SE-directed, progradational depositional system with the major source area provided by uplifted basement blocks, in particular by the Bornholm Block. Sediment progradation was enhanced by downfaulting along a strike-slip fault zone and related expansion of accommodation space. Closer to the Christiansø Block, some syn-tectonic deposition also took place and resulted in subtle thickness changes within the hinge zones of inversion-related growth folds. Lack of significant sediment supply from the inverted and uplifted offshore part of the Mid-Polish Trough suggests that in this area NW–SE-located marginal trough parallel to the inversion axis of the Mid-Polish Trough did not form, and that uplifted Bornholm Block played by far more prominent role for development of syn-inversion depositional successions.     

Origin of Dissolved Organic Carbon Studied by UV‐vis Spectroscopy

Dissolved organic carbon (DOC) distributions in water from Lake Ipê, MS, Brazil, were investigated. The samplings were performed monthly (surface, 1 m depth, and bottom) from June 1999 to June 2000. Absorbance at 285 nm and DOC concentrations in mg dm^—3, p(DOC), were highly correlated for the three depths. 77% of the surface, 85% for 1 m and bottom samples presented a variation between 20 dm³ g^—1 cm^—1 and 50 dm³ g^—1 cm^—1 of A(285 nm)/p(DOC), that characterizes the dissolved organic matter in lake water as essentially fulvic. The ratio A(254 nm)/p(DOC) was also sensitive for fulvic matter, and an A(250 nm)/A(365 nm) = 4 ratio was characteristic of strongly colored waters. The ratios A(436 nm)/p(DOC) for the three depths also showed a significant correlation. The predominance of fulvic acid is explained by environmental characteristics such as the tropical climate, temperatures above 18 °C, and the lake environment. It was demonstrated that the variation in the water carbon content due to different compartments in the lake can be monitored by UV‐vis spectroscopy ratios.     

Hydrogen isotope fractionation factor for mixed-layer illite/smectite at 60° to 150°C: new data from the northeast Texas Gulf Coast

The δD values of water and clay collected from 0.6 to 5.5 km deep wells in 9 oil and gas fields within the Houston salt basin located in the northeast Texas Gulf Coast were used to reevaluate the temperature dependence of hydrogen isotope fractionation between mixed layer illite/smectite (I/S) and water, and the equations of Yeh (1980), Geochim. Cosmochim. Acta, 42:140-143) and Capuano (1992), Geochim. Cosmochim. Acta, 56:2547-2554) for the calculation of αI/S-water, both of which are commonly cited in the literature. δD values of water and clay in the normally pressured and geopressured sections are different. In the normally pressured section (<2.6 km), δD_water is constant (−15 ± 1 (1σ)‰) while δD_clay increases linearly from −59 to −43‰ with increasing depth. In contrast, in the geopressured section δD_water decreases linearly from −7 to −26‰ with increasing depth while δD_clay is nearly constant (−36 ± 3 (1σ)‰). The opposite trends are a product of D/H exchange between clay and water in a water-dominated system within the normally pressured section and rock-dominated system in the geopressured section. Assuming hydrogen isotope equilibrium between sediments and enclosed pore water, the new δD_water and δD_clay data were used to calculate the hydrogen isotope fractionation factor between I/S and water (αI/S-water), which showed a good fit to the equation derived by Capuano (1992), but not to the equation derived by Yeh (1980), both for the normally and geopressured data despite that both data sets are strikingly different. This suggests that hydrogen isotope equilibrium has been achieved in these two different regimes and that the equation by Capuano (1992) is valid and has wider applicability.     

Secondary Ca–Al silicates in plutonic rocks: implications for their cooling history

Secondary Ca-Al silicates are used to constrain the P-T-x conditions of the very early post-magmatic stage of the intermediate to basic Hercynian plutonic complexes of Charroux-Civray (NW Massif Central, France) and Fichtelgebirge (NE Bavaria, Germany). The secondary Ca-Al silicates hydrogarnet, prehnite, pumpellyite, epidote and laumontite form lenses within unaltered or only slightly chloritized biotite. Hydrogarnet as the first occurring Ca-Al silicate phase crystallizes at temperatures above 340 °C. The common paragenesis prehnite + pumpellyite post-dates hydrogarnet and indicates rather narrow ranges of temperature (200-280 °C) and pressure (2-3 kbar). Laumontite is formed at the end of Ca-Al silicate crystallization (180-260 °C, 1-3 kbar), mostly in small fractures in association with prehnite and adularia. The observed crystallization sequence of the Ca-Al silicates and their stabilities define a retrograde alteration path for the plutonic rocks. The Ca-Al silicate assemblage results from an early pervasive alteration of the plutonic rocks by low X_CO2 fluids during post-magmatic cooling. Subsolidus cooling starts at about 4 kbar at solidus temperatures as indicated by magmatic epidote stability, hornblende barometry and fluid inclusion data, and continues under slightly decreasing pressure (uplift) down to 2-3 kbar at 200-280 °C (prehnite-pumpellyite paragenesis). This shows that Ca-Al silicate assemblages may be a unique tool to constrain the P-T conditions of the subsolidus cooling of intermediate to basic plutonic bodies.     

Bioassay‐directed fractionation for analyzing estrogens in surface waters of the German Baltic Sea

A reversed‐phase fractionation method with subsequent biological and chemical analysis has been developed to estimate the contributions of the most potent estrogens to observed estrogenic effect potentials. Surface water samples were taken in the German Baltic Sea (Inner Wismar Bay and Darss Peninsula, sampling campaign July 2003) and were separated into seven individual fractions. Three fractions showed significant estrogenic activities and clear dose‐dependant responses were obtained in the yeast estrogen screen (YES). In the 2nd fractions liquid chromatographic‐electrospray‐tandem mass spectrometric (LC‐ESI‐MS‐MS) analyses showed the presence of bisphenol A (Inner Wismar Bay: 4.8 ng L^–1 and 6 ng L^–1; Darss Peninsula: 0.91 ng L^–1 and 1.7 ng L^–1) and ethinylestradiol (Inner Wismar Bay: 2.0 ng L^–1 and 6.0 ng L^–1; Darss Peninsula: < MDL and 1.7 ng L^–1), whereas estrogenic activities in the YES were only around 10% of the positive control E2. Although not identified prior in the total extract the natural hormones estradiol (Inner Wismar Bay: 0.13 ng L^–1 and 0.19 ng L^–1; Darss Peninsula: 0.12 ng L^–1 and 0.16 ng L^–1) and estriol (Inner Wismar Bay: < MDL and 0.33 ng L^–1; Darss Peninsula: < MDL) could be detected in the 3rd fractions, where high estrogenic potentials could be observed. The 4th fractions showed high responses as well and estrone were herein quantified with concentrations of 0.16 ng L^–1 and 0.18 ng L^–1 (Darss Peninsula) up to 0.37 ng L^–1 (Inner Wismar Bay). Measured and calculated estradiol equivalents for individual fractions correlated very well (R² = 0.78), when disregarding results of the 2nd fraction, where high deviations occurred.     

Future extreme events in European climate: an exploration of regional climate model projections

This paper compares how well satellite versus weather station measurements of climate predict agricultural performance in Brazil, India, and the United States. Although weather stations give accurate measures of ground conditions, they entail sporadic observations that require interpolation where observations are missing. In contrast, satellites have trouble measuring some ground phenomenon such as precipitation but they provide complete spatial coverage of various parameters over a landscape. The satellite temperature measurements slightly outperform the interpolated ground station data but the precipitation ground measurements generally outperform the satellite surface wetness index. In India, the surface wetness index outperforms station precipitation but this may be reflecting irrigation, not climate. The results suggest that satellites provide promising measures of temperature but that ground station data may still be preferred for measuring precipitation in rural settings.     

Non‐Matrix‐Matched Calibration for the Multi‐Element Analysis of Geological and Environmental Samples Using 200 nm Femtosecond LA‐ICP‐MS: A Comparison with Nanosecond Lasers

LA‐ICP‐MS is one of the most promising techniques for in situ analysis of geological and environmental samples. However, there are some limitations with respect to measurement accuracy, in particular for volatile and siderophile/chalcophile elements, when using non‐matrix‐matched calibration. We therefore investigated matrix‐related effects with a new 200 nm femtosecond (fs) laser ablation system (NWRFemto200) using reference materials with different matrices and spot sizes from 10 to 55 μm. We also performed similar experiments with two nanosecond (ns) lasers, a 193 nm excimer (ESI NWR 193) and a 213 nm Nd:YAG (NWR UP‐213) laser. The ion intensity of the 200 nm fs laser ablation was much lower than that of the 213 nm Nd:YAG laser, because the ablation rate was a factor of about 30 lower. Our experiments did not show significant matrix dependency with the 200 nm fs laser. Therefore, a non‐matrix‐matched calibration for the multi‐element analysis of quite different matrices could be performed. This is demonstrated with analytical results from twenty‐two international synthetic silicate glass, geological glass, mineral, phosphate and carbonate reference materials. Calibration was performed with the certified NIST SRM 610 glass, exclusively. Within overall analytical uncertainties, the 200 nm fs LA‐ICP‐MS data agreed with available reference values.