(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Modelling of chloride transport in non-saturated concrete : from microscale to macroscale

A model for chloride transport in concrete is proposed. The model accounts for transport several transport mechanisms such as diffusion, advection, migration, etc. This work shows the chloride transport equations at the macroscopic scale in non-saturated concrete. The equations involve diffusion, migration, capillary suction, chloride combination and precipitation mechanisms. The material is assumed to be infinitely rigid, though the porosity can change under influence of chloride binding and precipitation. The involved microscopic and macroscopic properties of the materials are measured by standardized methods. The variables which must be imposed on the boundaries are temperature, relative humidity and chloride concentration. The output data of the model are the free, bound, precipitated and total chloride ion concentrations, as well as the pore solution content and the porosity. The proposed equations are solved by means of the finite element method (FEM) implemented in MATLAB (classical Galerkin formulation and the streamline upwind Petrov-Galerkin (SUPG) method to avoid spatial instabilities for advection dominated flows).

Cover cracking of the reinforced concrete due to rebar corrosion induced by chloride penetration

Este artículo estudia el proceso de fisuración del hormigón por corrosión de la armadura. Se presenta un modelo de transporte de cloruros en el hormigón, que contempla la no-linealidad de los coeficientes de difusión, las isotermas de absorción y el fenómeno de convección. A partir de los resultados de penetración de cloruros, se establece la corrosión de la armadura con la consiguiente expansión radial. La fisuración del hormigón se estudia con un modelo de fisura embebida. Los dos modelos (iniciación y propagación) se incorporan en un programa de elementos finitos. El modelo se contrasta con resultados experimentales, obteniéndose un buen ajuste. Una de las dificultades es establecer el umbral de concentración de cloruros que da lugar al inicio de la corrosión de la armadura.This paper is focused on the chloride-induced corrosion of the rebar in RC. A comprehensive model for the chloride ingress into concrete is presented, with special attention to non-linear diffusion coefficients, chloride binding isotherms and convection phenomena. Based on the results of chloride diffusion, subsequent active corrosion is assumed and the radial expansion of the corroded reinforcement reproduced. For cracking simulation, the Strong Discontinuity Approach is applied. Both models (initiation and propagation corrosion stages) are incorporated in the same finite element program and chained. Comparisons with experimental results are carried out, with reasonably good agreements being obtained, especially for cracking patterns. Major limitations refer to difficulties to establish precise levels of basic data such as the chloride ion content at concrete surface, the chloride threshold concentration that triggers active corrosion, the rate of oxide production or the rust mechanical properties.

Cover cracking of reinforced concrete due to rebar corrosión induced by chloride penetration

Este artículo estudia el proceso de fisuración del hormigón por corrosión de la armadura. Se presenta un modelo de transporte de cloruros en el hormigón, que contempla la no-linealidad de los coeficientes de difusión, las isotermas de absorción y el fenómeno de convección. A partir de los resultados de penetración de cloruros, se establece la corrosión de la armadura con la consiguiente expansión radial. La fisuración del hormigón se estudia con un modelo de fisura embebida. Los dos modelos (iniciación y propagación) se incorporan en un programa de elementos finitos. El modelo se contrasta con resultados experimentales, obteniéndose un buen ajuste. Una de las dificultades es establecer el umbral de concentración de cloruros que da lugar al inicio de la corrosión de la armadura.This paper is focused on the chloride-induced corrosion of the rebar in RC. A comprehensive model for the chloride ingress into concrete is presented, with special attention to non-linear diffusion coefficients, chloride binding isotherms and convection phenomena. Based on the results of chloride diffusion, subsequent active corrosion is assumed and the radial expansion of the corroded reinforcement reproduced. For cracking simulation, the Strong Discontinuity Approach is applied. Both models (initiation and propagation corrosion stages) are incorporated in the same finite element program and chained. Comparisons with experimental results are carried out, with reasonably good agreements being obtained, especially for cracking patterns. Major limitations refer to difficulties to establish precise levels of basic data such as the chloride ion content at concrete surface, the chloride threshold concentration that triggers active corrosion, the rate of oxide production or the rust mechanical properties.

Presence of Siloxanes in the Biogas of a Wastewater Treatment Plant Separation in Condensates and Influence of the Dose of Iron Chloride on its Elimination

The siloxanes present in the biogas produced during anaerobic digestion damage the mechanism of cogeneration equipment and, consequently, negatively affect the energy valorization process. For this reason, the detection and elimination of these silicon-derived chemical compounds are a priority in the management of cogeneration facilities. In this regard, the objectives of this paper are, firstly, to characterize the siloxanes in the biogas and, secondly, to qualitatively evaluate the influence of the dose of iron chloride on its elimination. The research was performed at the Rincón de León Wastewater Treatment Plant (Alicante, Spain). The outflow biogas of the digesters and of the pressurized gasometers was sampled and analyzed. The results obtained made it possible to demonstrate, firstly, the absence of linear siloxanes and that, of the cyclic siloxanes, the predominant type was decamethylcyclopentasiloxane, and, secondly, that the addition of iron chloride in the digesters significantly reduces the siloxane content in the biogas. Additionally, it was demonstrated that the process of compression of the biogas, with the elimination of condensates, also produces significant reductions in the concentration of siloxanes in the biogas.

Acute cadmium chloride administration induces hepatic and renal CYP2A5 mRNA, protein and activity in the mouse: involvement of transcription factor NRF2

Modulation of the cytochrome P450 (CYP) monooxygenase system by cadmium was investigated in male, adult DBA/2J mice treated with a single dose (16 mumol/kg body weight, i.p.) of cadmium chloride (CdCl2). Total CYP content of liver and kidney microsomes decreased maximally (56% and 85%, respectively) 24 and 18 h, respectively, after CdCl2 treatment. Progressive increases of hepatic coumarin 7-hydroxylase (COH) activity; indicative of CYP2A5 activity, relative to the total CYP content were seen at 8 h (2-fold), 12 h (3-fold), 18 h (12-fold), and 24 h (15-fold). Similar changes were seen in the kidney. Liver and kidney CYP2A5 mRNA levels increased maximally 12 and 4 h after treatment and decreased to almost half 6 h later. In contrast, kidney and liver CYP2A5 protein levels increased maximally at 18 and 24 h. The CYP2A5 mRNA levels in the kidney and liver increased after Cd treatment in Nrf2 +/+ but not in Nrf2 -/- mouse. This study demonstrates that hepatic and kidney CYP2A5 is upregulated by cadmium with a somewhat faster response in the kidney than the liver. The strong upregulation of the CYP2A5 both at mRNA and enzyme activity levels, with a simultaneous decrease in the total CYP concentration suggest an unusual mode of regulation of CYP2A5 in response to cadmium exposure, amongst the CYP enzymes. The observed decrease in the mRNA but not in protein levels after maximal induction may suggest involvement of post-trancriptional mechanisms in the regulation. Upregulation of CYP2A5 by cadmium in the Nrf2 +/+ mice but not in the Nrf2 -/- mice indicates a role for this transcription factor in the regulation. (C) 2003 Elsevier Ireland Ltd. All rights reserved.

Novel one-dimensional structures and solution behaviour of copper(II) bromide and chloride complexes of a new pentapyridyldiamine ligand

Copper(II) bromide and chloride complexes of the new heptadentate ligand 2,6-bis(bis(2-pyridylmethyl)amino)methylpyridine (L) have been prepared. For the bromide complexes, chains of novel, approximately C-2-symmetric, chiral [Cu-2(L)Br-2](2+) 'wedge-shaped' tectons are found. The links between the dicopper tectons and the overall chirality and packing of the chains are dictated by the bromide ion content, not the counter anion. In contrast, the chloride complexes exhibit linked asymmetric [Cu-2(L)Cl-3](+) tectons with distinct N3CuCl2 and N4CuCl2 centres in the solid. The overall structures of the dicopper bromide and chloride units persist in solution irrespective of the halide. The redox chemistry of the various species is also described.

Acute cadmium chloride administration induces hepatic and renal cytochrome P450 2A5 in the mouse

Modulation of the cytochrome P450 (CYP) monooxygenase system by cadmium was investigated in male, adult DBA/2J mice treated with a single dose (16 Amol/kg body weight, i.p.) of cadmium chloride (CdCl2) at various time points. The total CYP content of kidney microsomes started to decrease 4 hours earlier than in the liver (P < 0.05), with maximal decreases at 24 hours of 56% and 85% in the liver and kidney, respectively. In contrast, both hepatic and renal coumarin 7-hydroxylase (COH) activity (indicative of CYP2A5 activity) relative to total CYP content started to progressively increase at 8 hours, with renal activity 61 times higher than the hepatic activity. Maximum increases were observed, 15-fold in the liver and 64-fold in the kidney after 24 hours. Liver and kidney CYP2A5 mRNA levels increased maximally 12 and 4 hours after treatment, respectively and decreased to almost half 6 hours later. In contrast, kidney and liver CYP2A5 protein levels increased maximally at 18 and 24 hours. This study demonstrates that hepatic and renal CYP2A5 is upregulated by cadmium with a faster response in the kidney than in the liver. This observation is concordant with the fact that kidney is the target organ for cadmium toxicity. The observed increase in the mRNA but not in protein levels after maximal induction suggests involvement of post-transcriptional mechanisms in the regulation of CYP2A5 expression by cadmium.

Chloride as a signature indicator of soil textural and hydrologic stratigraphies in variable charge deep profiles

Soil properties that influence water movement through profiles are important for determining flow paths, reactions between soil and solute, and the ultimate destination of solutes. This is particularly important in high rainfall environments. For highly weathered deep profiles, we hypothesize that abrupt changes in the distribution of the quotient [QT = (silt + sand)/clay] reflect the boundaries between textural units or textural (TS) and hydrologic (HS) stratigraphies. As a result, QT can be used as a parameter to characterize TS and as a surrogate for HS. Secondly, we propose that if chloride distributions were correlated with QT, under non-limiting anion exchange, then chloride distributions can be used as a signature indicator of TS and HS. Soil cores to a depth of 12.5 in were taken from 16 locations in the wet tropical Johnstone River catchment of northeast Queensland, Australia. The cores belong to nine variable charge soil types and were under sugarcane (Saccharun officinarum-S) production, which included the use of potassium chloride, for several decades. The cores were segmented at I m depth increments and subsamples were analysed for chloride, pH, soil water content (theta), clay, silt and sand contents. Selected bores were capped to serve as piezometers to monitor groundwater dynamics. Depth incremented QT, theta and chloride correlated, each individually, significantly with the corresponding profile depth increments, indicating the presence of textural, hydrologic and chloride gradients in profiles. However, rapid increases in QT down the profile indicated abrupt changes in TS, suggesting that QT can be used as a parameter to characterize TS and as a surrogate for HS. Abrupt changes in chloride distributions were similar to QT, suggesting that chloride distributions can be used as a signature indicator of QT (TS) and HS. Groundwater data indicated that chloride distributions depended, at least partially, on groundwater dynamics, providing further support to our hypothesis that chloride distribution can be used as a signature indicator of HS. Copyright (c) 2005 John Wiley & Sons, Ltd.

(Table 1) Results of pore water analyses, including boron content and boron isotope ratios

Drilling a transect of holes across the Costa Rica forearc during ODP Leg 170 demonstrated the margin wedge to be of continental, non accretionary origin, which is intersected by permeable thrust faults. Pore waters from four drillholes, two of which penetrated the décollement zone and reached the underthrust lower plate sedimentary sequence of the Cocos Plate, were examined for boron contents and boron isotopic signatures. The combined results show dilution of the uppermost sedimentary cover of the forearc, with boron contents lower than half of the present-day seawater values. Pore fluid "refreshening" suggests that gas hydrate water has been mixed with the sediment interstitial water, without profoundly affecting the d11B values. Fault-related flux of a deeply generated fluid is inferred from high B concentration in the interval beneath the décollement, being released from the underthrust sequence with incipient burial. First-order fluid budget calculations over a cross-section across the Costa Rica forearc indicate that no significant fluid transfer from the lower to the upper plate is inferred from boron fluid profiles, at least within the frontal 40 km studied. Expulsed lower plate pore water, which is estimated to be 0.26-0.44 km3 per km trench, is conducted efficiently along and just beneath the décollement zone, indicating effective shear-enhanced compaction. In the upper plate forearc wedge, dewatering occurs as diffuse transport as well as channelled flow. A volume of approximately 2 km3 per km trench is expulsed due to compaction and, to a lesser extent, lateral shortening. Pore water chemistry is influenced by gas hydrate instability, so that it remains unknown whether deep processes like mineral dehydration or hydrocarbon formation may play a considerable role towards the hinterland.