Physicochemical properties of electrostatically crosslinked carrageenan/chitosan hydrogels and carrageenan/chitosan/Laponite nanocomposite hydrogels.

In this work physical carrageenan/chitosan (Car/Chit) hydrogels are prepared by electrostatic complexation between the two oppositely charged polysaccharides. The hydrogels have storage moduli in the order of 5-10 kPa and swelling ratios in the order of 5000-6000 %. At conditions where both polysaccharides are highly charged (pH 5) the swelling ratios are lower than the ones at conditions of lower dissociation i.e., at pH 2 and 7 and the opposite trend is found for the storage modulus. Chit appears to act as a crosslinker for Car as increasing its concentration the swelling ratio decreases and the moduli increase. The hydrogels can incorporate the nanoclay Laponite (Lap) and form hybrid nanocomposites where the intercalation by the two biopolymers leads to exfoliation of the clay nanoplatelets in the presence of both Car and Chit. The composite hydrogels retain the mechanical properties of the Car/Chit hydrogels at the studied pH range (pH 2 to pH 7). This shows the prepared hydrogels can be potentially used as multifunctional biomaterials for drug delivery, tissue engineering and bone regeneration applications.

Chromium speciation, mobility, and Cr(VI) retention-release processes in ultramafic rocks and Fe-Ni lateritic deposits of Greece.

Water contamination by geogenic hexavalent chromium is an emerging issue in areas developed on ultramafic rocks and their weathering products. In this study, samples of serpentinites, soil, and laterites were collected and analyzed for the levels of Cr species, distribution into phases of different mobility, mineralogy, Cr oxidation capacity, and leaching of Cr(VI). Total chromium (2176-21,929 mg kg-1) was mainly found in Cr spinels (~ 50% wt as Cr2O3) and Fe (hydr)oxides (2.5% wt). Total Cr(VI) contents (0.49-11.5 mg kg-1) increased from the serpentinites to the soil and lateritic deposit, i.e., during the advanced stages of weathering, which were accompanied by increased Cr mobility. Batch experiments of 500-h duration showed that Cr(VI) released in water at rates of 0.25-1.20 nM h-1. Rates were higher in water of pH 5.7 rather than pH 8.5, because more Cr(VI) was formed during the experimental period. Asbolane-type Mn oxides and Mn-bearing crystalline Fe oxides were responsible for Cr(III) oxidation. Most of the generated Cr(VI) (52-79% of total Cr(VI)) remained solid-bound by adsorption and/or precipitation processes. Because all samples had a self-capacity to oxidize Cr(III), it seems that retention processes will ultimately define the extent of geogenic Cr(VI) contamination of aquatic systems.

Evidence for photochemical production of reactive oxygen species in desert soils.

The combination of intense solar radiation and soil desiccation creates a short circuit in the biogeochemical carbon cycle, where soils release significant amounts of CO2 and reactive nitrogen oxides by abiotic oxidation. Here we show that desert soils accumulate metal superoxides and peroxides at higher levels than non-desert soils. We also show the photogeneration of equimolar superoxide and hydroxyl radical in desiccated and aqueous soils, respectively, by a photo-induced electron transfer mechanism supported by their mineralogical composition. Reactivity of desert soils is further supported by the generation of hydroxyl radical via aqueous extracts in the dark. Our findings extend to desert soils the photogeneration of reactive oxygen species by certain mineral oxides and also explain previous studies on desert soil organic oxidant chemistry and microbiology. Similar processes driven by ultraviolet radiation may be operating in the surface soils on Mars.