Influence of TiO2 pigment particles on chromate ion transport in epoxy films

Transport of active species (i.e., ions) leaching from pigment particles incorporated in a polymer matrix is the main mechanism behind the anticorrosive performance of protective coatings. Understanding this mechanism is necessary for the effective design of the systems utilizing pigments less toxic than the most efficient chromate salts. It was demonstrated that anticorrosive pigment particles can themselves facilitate the transport of active species via the pathways formed after pigment leaching from a coating. It was also suggested that other paint components, e.g., certain additives, pigments, and fillers can be involved in the formation of transport pathways. Investigation of the possible influence of inert pigment (TiO2) on creating the pathways for chromate ion transport in polymer coatings was the primary objective of this work. In an experiment mimicking the transport of pigment species (i.e., chromate ions), a model epoxy coating containing particles of a single pigment (TiO2) was exposed to a chromate solution (aqueous, or with the addition of acetone as a polymer swelling agent). It was shown that the chromate ions can be transported in the epoxy film preferentially via the TiO2 particles/polymer matrix interface.

Elimination of Chromium (VI) by Adsorption onto Natural and/or Modified Kaolinite

The purpose of this study is to compare the effectiveness of a natural and / or modified kaolinite to adsorb chromium-containing aqueous effluents in its most toxic form (the hexavalent chromate ion (Cr (VI)). Adsorbant used in the present study is a kaolinite of hydrothermal origin. The modified kaolinite has been prepared by insertion of a cationic surfactant DTAC in interlayer space of this clay. The modification method is generally performed by the cation exchange reaction in the liquid state. The specific surface areas determined by nitrogen adsorption at 77 K for the two samples of kaolinite (natural and modified) are succinctly 48.75 and 63.72 m2/g. Scanning electron microscopy has shown that the used clay is in tubular form. The treatment of natural kaolin by the intercalation of cationic surfactant increased its specific surface of about 18 %. Therefore its power sorptif increased which was found by a comparative study of adsorption of Cr (VI) on natural kaolin and / or modified.

A systematic look at chromium isotopes in modern shells – implications for paleo-environmental reconstructions

The chromium isotope system (53Cr ∕ 52Cr, expressed as δ53Cr relative to NIST SRM 979) in marine biogenic and non-biogenic carbonates is currently being evaluated as a proxy for the redox state of the ocean. Previous work has concentrated on using corals and foraminifera for this purpose, but investigations focusing on the behavior of Cr in bivalves as potential archives are lacking. Due to their often good preservation, fossil marine biogenic carbonates have the potential to serve as useful archives for the reconstruction of past ocean redox fluctuations and eventually link those to climatic changes throughout Earth's history. Here, we present an evaluation of the Cr isotope system in shells of some modern bivalves. Shell species from Lucidinadae, Cardiidae, Glycimerididae and Pectenidae, collected systematically from one Mediterranean location (Playa Poniente, Benidorm, Spain) over a 3-year period reveal δ53Cr values ranging from 0.15 ‰ to 0.65 ‰, values that are systematically below the local seawater δ53Cr value of 0.83±0.05 ‰. This attests to a significant reduction of dissolved seawater chromium in the process leading to calcification and thus for control of Cr isotope fractionation during biological routes. A similar, constant offset in δ53Cr values relative to surface seawater is observed in shells from Mytilius edulis from an arctic location (Godhavn, Disko Bay, Greenland). Chromium concentrations in the studied shells are significantly controlled by organic matter and typically range from 0.020 to 0.100 ppm, with some higher concentrations of up to 0.163 ppm recorded in Pectenidae. We also observe subtle, species-dependent differences in average Cr isotope signatures in the samples from Playa Poniente, particularly of Lucidinadae and Cardiidae, with considerably depressed and elevated δ53Cr values, respectively, relative to the other species investigated. Intra-species heterogeneities, both in Cr concentrations and δ53Cr values, are favorably seen to result from vital effects during shell calcification rather than from heterogeneous seawater composition. This is because we observe that the surface seawater composition in the particular Playa Poniente location remained constant during the month of July of the 3 years we collected bivalve samples. Intra-shell heterogeneities – associated with growth zones reflecting one to several years of growth, both in δ53Cr and Cr concentrations – are observed in a sample of Placuna placenta and Mimachlamys townsendi. We suspect that these variations are, at least partially, related to seasonal changes in δ53Cr of surface seawaters. Recognizing the importance of organic substances in the bivalve shells, we propose a model whereby reduction of Cr(VI) originally contained in the seawater as chromate ion and transported to the calcifying space, to Cr(III), is effectively adsorbed onto organic macromolecules which eventually get included in the growing shell carbonates. This study, with its definition of statistically sound offsets in δ53Cr values of certain bivalve species from ambient seawater, forms a base for future investigations aimed at using fossil shells as archives for the reconstruction of paleo-seawater redox fluctuations.

A systematic look at chromium isotopes in modern shells – implications for paleo-environmental reconstructions

The chromium isotope system (53Cr / 52Cr expressed as δ53Cr relative to NIST SRM 979) in marine biogenic and non-biogenic carbonates is currently being evaluated as a proxy for the redox state of the ocean. Previous work has concentrated on using corals and foraminifera for this purpose, but investigations focusing on the behavior of Cr in bivalves as potential archives are lacking. Due to their often good preservation, fossil marine biogenic carbonates have the potential to serve as useful archives for the reconstruction of past ocean redox fluctuations and eventually link those to climatic changes throughout Earth’s history. Here, we present an evaluation of the Cr isotope system in shells of some modern bivalves. Shell species from Lucidinadae, Cardiidae, Glycimerididae, and Pectenidae, collected systematically from one Mediterranean location (Playa Poniente, Benidorm, Spain) over a three year period, reveal δ53Cr values ranging from 0.15 to 0.65 ‰, values that are systematically below the local seawater δ53Cr value of 0.83 ± 0.05 ‰. This attests for significant reduction of dissolved seawater chromium in the process leading to calcification and thus for control of Cr isotope fractionation during biological routes. A similar, constant offset in δ53Cr values relative to surface seawater is observed in shells from Mytilius edulis from an arctic location (Godhavn, Disko Bay, Greenland). Chromium concentrations in the studied shells are significantly controlled by organic matter and typically range from 0.020 to 0.100 ppm, with some higher concentrations of up to 0.163 ppm recorded in Pectenidae. We also observe subtle, species-dependent differences in average Cr isotope signatures in the samples from Playa Poniente, particularly of Lucidinadae and Cardiidae, with considerably depressed and elevated δ53Cr values, respectively, relative to the other species investigated. Within-species heterogeneities, both in Cr concentrations and δ53Cr values, are favorably seen to result from vital effects during shell calcification rather than from heterogeneous seawater composition. This is because we observe that the surface seawater composition in the particular Playa Poniente location remained constant during July month of the three years we collected bivalve samples. Within single shell heterogeneities associated with growth zones reflecting one to several years of growth, both in δ53Cr and Cr concentrations, are observed in a sample of Placuna placenta and Mimachlamys townsendi. We suspect that these variations are, at least partially, related to seasonal changes in δ53Cr of surface seawaters. Recognizing the importance of organic substances in the bivalve shells, we propose a model whereby reduction of Cr(VI) originally contained in the seawater as chromate ion and transported to the calcifying space, to Cr(III), is effectively adsorbed onto organic macromolecules which eventually get included in the growing shell carbonates. This study, with its definition of statistically sound offsets in δ53Cr values of certain bivalve species from ambient seawater, forms a base for futures investigations aimed at using fossil shells as archives for the reconstruction of paleo-seawater redox fluctuations.