Adsorption Affinity of Linear and Aromatic Organic Anions Competing for Cationic Cement Surfaces.

Competitive adsorption of chemical admixtures onto cement is of critical importance in delivering bulk performance requirements of cement slurries employed in constructing high-performing structures, like oil wells. This challenge is complex to investigate, because of the many variables that include the heterogeneity, high pH, and ionic strength of cement fluids; the multiple crystalline phases present in unhydrated and set cement; and the high number of admixtures required to meet performance criteria in commercial operations. The purpose of this study is to relate chemical structures to relative adsorption behavior of admixtures onto cement when present together and classify such interactions as beneficial (synergistic) or detrimental (antagonistic). Adsorption characteristics of single admixtures were examined by total organic carbon analysis, FT infrared spectroscopy, scanning electron microscopy, calorimetry, and UV/vis spectrophotometry. Results show that the adsorption of single chemical admixtures follows the order of monomeric hydroxycarboxylate molecule > sulfonated linear polymer > sulfonated aromatic polymer > carboxylated/sulfonated linear polymer > carboxylated branched polyether polymers. The observed adsorption behavior of polymers correlates extremely well with the order for cement hydration retardation, with carboxylated polymers being the most powerful retarders. Results correlate closely with the proposed mechanism that sulfonated polymers adsorb onto aluminate phases, presumably the tricalcium aluminate phase; and the carboxylate polymers onto silicate phases, particularly the predominant tricalcium oxysilicate phase. The hydroxycarboxylic monomeric molecule was the strongest retarder of all and has the highest adsorption level, presumably on tricalcium oxysilicate. The competitive adsorption behavior in binary mixtures was studied by monitoring the displacement of a signaling polymer by a second admixture. Results indicate that, for similar functional groups, shorter polymers are competitively more strongly adsorbed than longer chain molecules and that the shorter chain polymers were not desorbed significantly by longer chain polymer molecules. Rheological measurements correlated admixture adsorption behavior to the observed slurry fluidity.

Toxicity of quantum dots and cadmium salt to Caenorhabditis elegans after multigenerational exposure.

To fully understand the biological and environmental impacts of nanomaterials requires studies that address both sublethal end points and multigenerational effects. Here, we use a nematode to examine these issues as they relate to exposure to two different types of quantum dots, core (CdSe) and core-shell (CdSe/ZnS), and to compare the effect to those observed after cadmium salt exposures. The strong fluorescence of the core-shell QDs allowed for the direct visualization of the materials in the digestive track within a few hours of exposure. Multiple end points, including both developmental and locomotive, were examined at QD exposures of low (10 mg/L Cd), medium (50 mg/L Cd), and high concentrations (100 mg/L Cd). While the core-shell QDs showed no effect on fitness (lifespan, fertility, growth, and three parameters of motility behavior), the core QDs caused acute effects similar to those found for cadmium salts, suggesting that biological effects may be attributed to cadmium leaching from the more soluble QDs. Over multiple generations, we commonly found that for lower life-cycle exposures to core QDs the parents response was generally a poor predictor of the effects on progeny. At the highest concentrations, however, biological effects found for the first generation were commonly similar in magnitude to those found in future generations.

Size-dependent impacts of silver nanoparticles on the lifespan, fertility, growth, and locomotion of Caenorhabditis elegans.

The increased bioavailability of nanoparticles engineered for good dispersion in water may have biological and environmental impacts. To examine this issue, the authors assessed the biological effects in nematodes as they relate to exposure to silver nanoparticles (AgNPs) of different sizes at low (1 mg/L Ag), medium (10 mg/L Ag), and high concentrations (100 mg/L Ag). Over multiple generations, the authors found that the smallest particle, at 2 nm, had a notable impact on nematode fertility. In contrast, the largest particle, at 10 nm, significantly reduced the lifespan of parent nematodes (P0 ) by 28.8% and over the span of 3 generations (F1 -F3). In addition, a computer vision system automatically measured the adverse effects in body length and motility, which were not size-dependent.

t4 workshop report. Nanotoxicology: "the end of the beginning" - signs on the roadmap to a strategy for assuring the safe application and use of nanomaterials.

In October 2010, a group of experts met as part of the transatlantic think tank for toxicology (t4) to exchange ideas about the current status and future of safety testing of nanomaterials. At present, there is no widely accepted path forward to assure appropriate and effective hazard identification for engineered nanomaterials. The group discussed needs for characterization of nanomaterials and identified testing protocols that incorporate the use of innovative alternative whole models such as zebrafish or C. elegans, as well as in vitro or alternative methods to examine specific functional pathways and modes of action. The group proposed elements of a potential testing scheme for nanomaterials that works towards an integrated testing strategy, incorporating the goals of the NRC report Toxicity Testing in the 21st Century: A Vision and a Strategy by focusing on pathways of toxic response, and utilizing an evidence-based strategy for developing the knowledge base for safety assessment. Finally, the group recommended that a reliable, open, curated database be developed that interfaces with existing databases to enable sharing of information.