Quantitative Analysis of Heavy Metals in Children’s Toys and Jewelry: A Multi-Instrument, Multi-Technique Exercise in Analytical Chemistry and Public Health

For most chemistry curricula, laboratory-based activities in quantitative and instrumental analysis continue to be an important aspect of student development/training, one that can be more effective if conceptual understanding is delivered through an inquiry-based process relating the material to relevant issues of public interest and student career trajectories. Laboratory experiences that actively engage students in this manner can be difficult to identify and execute. A special topics, project-based laboratory module is presented here that utilizes multiple techniques and instruments to investigate toxic metal content (lead, cadmium, and arsenic) in children’s toys and toy jewelry. The module effectively illustrates a considerable number of fundamental and advanced quantitative analysis principles including sample digestion, Beer–Lambert law, calibration curve, and standard addition analyses, as well as instrumental analysis considerations of atomic absorption spectroscopy including atomization efficiency (e.g., flames vs furnaces), matrix modifiers, and nondestructive spectroscopy. Module effectiveness stems from the illustration of critical chemical analysis principles in the context of projects with student-directed hypotheses and experimental results that are clearly relevant to the interface of basic science, medicine, and public health: primary career interests for a significant number of undergraduates in the physical and life sciences

Stable Aqueous Nanoparticle Film Assemblies with Covalent and Charged Polymer Linking Networks

The construction of highly stable and efficiently assembled multilayer films of purely water soluble gold nanoparticles is reported. Citrate-stabilized nanoparticles (CS-NPs) of average core diameter of 10 nm are used as templates for stabilization-based exchange reactions with thioctic acid to form more robust aqueous NPs that can be assembled into multilayer films. The thioctic acid stabilized nanoparticles (TAS-NPs) are networked via covalent and electrostatic linking systems, employing dithiols and the cationic polymer poly(l-lysine), respectively. Multilayer films of up to 150 nm in thickness are successfully grown at biological pH with no observable degradation of the NPs within the film. The characteristic surface plasmon band, an optical feature of certain NP film assemblies that can be used to report the local environment and core spacing within the film, is preserved. Growth dynamics and film stability in solution and in the air are examined, with poly(l-lysine) linked films showing no evidence of aggregation for at least 50 days. We believe these films represent a pivotal step toward exploring the potential of aqueous NP film assemblies as a sensing apparatus

Magmatically folded and faulted schlieren zones formed by magma avalanching in the Sonora Pass Intrusive Suite, Sierra Nevada, California

The southwestern margin of the Late Cretaceous Sonora Pass Intrusive Suite, northern Sierra Nevada, California (USA), preserves a densely populated zone of magmatic structures that record dynamic magmatic layer formation and deformation (faulting and folding) within a solidifying upper-crustal magma mush. This zone consists largely of coupled melanocratic (or schlieren) and leucocratic bands hosted within the 95.6 ± 1.5 Ma Kinney Lakes granodiorite (Leopold, 2016), with orientations approximately parallel to the intrusive margin and with inward younging directions. Schlieren consist of a high modal abundance of medium-grained ferromagnesian minerals (hornblende + biotite), zircon, sphene, apatite, opaque minerals, and minor plagioclase and interstitial quartz. Leucocratic bands are dominated by coarse-grained feldspar + quartz with minor ferromagnesian and accessory minerals. Whole-rock geochemical and Sr and Nd isotopic data indicate that the schlieren are derived from the Kinney Lakes granodiorite by effective mechanical separation of mafic minerals and accessory phases. We interpret that the schlieren zone at the margin of the Kinney Lakes granodiorite formed by large-scale collapse of crystal mush by “magma avalanching,” facilitated by gravity, local convection, and possibly by host-rock stoping at the margin. This process eroded a significant portion of the solidifying margin of the chamber and resulted in the formation of magmatically deformed layered structures, which experienced further mingling, re-intrusion, magmatic erosion, and recycling processes. We envisage that magma avalanching of magma mushes in plutons can be achieved by any unstable process (e.g., tectonic, fluid-assisted, stoping, or gravity-driven) in large, longlived magma-mush chambers.Fil: Alasino, Pablo Horacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Regional de Investigaciones Científicas y Transferencia Tecnológica de La Rioja. - Universidad Nacional de La Rioja. Centro Regional de Investigaciones Científicas y Transferencia Tecnológica de La Rioja. - Universidad Nacional de Catamarca. Centro Regional de Investigaciones Científicas y Transferencia Tecnológica de La Rioja. - Secretaría de Industria y Minería. Servicio Geológico Minero Argentino. Centro Regional de Investigaciones Científicas y Transferencia Tecnológica de La Rioja. - Provincia de La Rioja. Centro Regional de Investigaciones Científicas y Transferencia Tecnológica de La Rioja; ArgentinaFil: Ardill, K.. University of Southern California; Estados UnidosFil: Stanback, J.. University of Southern California; Estados UnidosFil: Paterson, Scott Robert. University of Southern California; Estados UnidosFil: Galindo, C.. Universidad Complutense de Madrid; EspañaFil: Leopold, M.. San Juan College; Estados Unidos. School of Science, Math, and Engineering; Estados Unido

Multi-technique Quantitative Analysis and Socioeconomic Considerations of Lead, Cadmium, and Arsenic in Children\u27s Toys and Toy Jewelry

A wide spectrum and large number of children’s toys and toy jewelry items were purchased from both bargain and retail vendors and analyzed for arsenic, cadmium, and lead metal content using multiple analytical techniques, including flame and furnace atomic absorption spectroscopy as well as X-ray fluorescence spectroscopy. Particularly dangerous for young children, metal concentrations in toys/toy jewelry were assessed for compliance with current Consumer Safety Product Commission (CPSC) regulations (F963-11). A conservative metric involving multiple analytical techniques was used to categorize compliance: one technique confirmation of metal in excess of CPSC limits indicated a “suspect” item while confirmation on two different techniques warranted a non-compliant designation. Sample matrix-based standard addition provided additional confirmation of non-compliant and suspect products. Results suggest that origin of purchase, rather than cost, is a significant factor in the risk assessment of these materials with 57% of toys/toy jewelry items from bargain stores non-compliant or suspect compared to only 15% from retail outlets and 13% if only low cost items from the retail stores are compared. While jewelry was found to be the most problematic product (73% of non-compliant/suspect samples), lead (45%) and arsenic (76%) were the most dominant toxins found in non-compliant/suspect samples. Using the greater Richmond area as a model, the discrepancy between bargain and retail children’s products, along with growing numbers of bargain stores in low-income and urban areas, exemplifies an emerging socioeconomic public health issue

Electrochemical Characterization of Self-Assembled Monolayers on Gold Substrates Derived from Thermal Decomposition of Monolayer-Protected Cluster Films

Networked films of monolayer-protected clusters (MPCs), alkanethiolate-stabilized gold nanoparticles, can be thermally decomposed to form stable gold on glass substrates that are subsequently modified with self-assembled monolayers (SAMs) for use as modified electrodes. Electrochemical assessment of these SAM-modified gold substrates, including double-layer capacitance measurements, linear sweep desorption of the alkanethiolates, and diffusional redox probing, all show that SAMs formed on gold supports formed from thermolysis of MPC films possess substantially higher defect density compared to SAMs formed on traditional evaporated gold. The density of defects in the SAMs on thermolyzed gold is directly related to the strategies used to assemble the MPC film prior to thermolysis. Specifically, gold substrates formed from thermally decomposing MPC films formed with electrostatic bridges between carboxylic acid-modified MPCs and metal ion linkers are particularly sensitive to the degree of metal exposure during the assembly process. While specific metal dependence was observed, metal concentration within the MPC precursor film was determined to be a more significant factor. Specific MPC film linking strategies and pretreatment methods that emphasized lower metal exposure resulted in gold films that supported SAMs of lower defect density. The defect density of a SAM-modified electrode is shown to be critical in certain electrochemical experiments such as protein monolayer electrochemistry of adsorbed cytochrome c. While the thermal decomposition of nanoparticle film assemblies remains a viable and interesting technique for coating both flat and irregular shaped substrates, this study provides electrochemical assessment tools and tactics for determining and controlling SAM defect density on this type of gold structure, a property critical to their effective use in subsequent electrochemical applications

High Resolution He-like Argon And Sulfur Spectra From The PSI ECRIT

We present new results on the X-ray spectroscopy of multicharged argon, sulfur and chlorine obtained with the Electron Cyclotron Resonance Ion Trap (ECRIT) in operation at the Paul Scherrer Institut (Villigen, Switzerland). We used a Johann-type Bragg spectrometer with a spherically-bent crystal, with an energy resolution of about 0.4 eV. The ECRIT itself is of a hybrid type, with a superconducting split coil magnet, special iron inserts which provides the mirror field, and a permanent magnetic hexapole. The high frequency was provided by a 6.4 GHz microwave emitter. We obtained high intensity X-ray spectra of multicharged F-like to He-like argon, sulfur and chlorine with one 1s hole. In particular, we observed the 1s2s^{3}S_1 \to 1s^2^{1}S_0 M1 and 1s2p^{3}P_2 \to 1s^2^{1}S_0 M2 transitions in He-like argon, sulfur and chlorine with unprecedented statistics and resolution. The energies of the observed lines are being determined with good accuracy using the He-like M1 line as a reference

Early specific cognitive-behavioural psychotherapy in subjects at high risk for bipolar disorders: study protocol for a randomised controlled trial

Background: Bipolar disorders (BD) are among the most severe mental disorders with first clinical signs and symptoms frequently appearing in adolescence and early adulthood. The long latency in clinical diagnosis (and subsequent adequate treatment) adversely affects the course of disease, effectiveness of interventions and health-related quality of life, and increases the economic burden of BD. Despite uncertainties about risk constellations and symptomatology in the early stages of potentially developing BD, many adolescents and young adults seek help, and most of them suffer substantially from symptoms already leading to impairments in psychosocial functioning in school, training, at work and in their social relationships. We aimed to identify subjects at risk of developing BD and investigate the efficacy and safety of early specific cognitive-behavioural psychotherapy (CBT) in this subpopulation. Methods/Design: EarlyCBT is a randomised controlled multi-centre clinical trial to evaluate the efficacy and safety of early specific CBT, including stress management and problem solving strategies, with elements of mindfulness-based therapy (MBT) versus unstructured group meetings for 14 weeks each and follow-up until week 78. Participants are recruited at seven university hospitals throughout Germany, which provide in-and outpatient care (including early recognition centres) for psychiatric patients. Subjects at high risk must be 15 to 30 years old and meet the combination of specified affective symptomatology, reduction of psychosocial functioning, and family history for (schizo) affective disorders. Primary efficacy endpoints are differences in psychosocial functioning and defined affective symptomatology at 14 weeks between groups. Secondary endpoints include the above mentioned endpoints at 7, 24, 52 and 78 weeks and the change within groups compared to baseline; perception of, reaction to and coping with stress; and conversion to full BD. Discussion: To our knowledge, this is the first study to evaluate early specific CBT in subjects at high risk for BD. Structured diagnostic interviews are used to map the risk status and development of disease. With our study, the level of evidence for the treatment of those young patients will be significantly raised

Coarse grained description of the protein folding

We consider two- and three-dimensional lattice models of proteins which were characterized previously. We coarse grain their folding dynamics by reducing it to transitions between effective states. We consider two methods of selection of the effective states. The first method is based on the steepest descent mapping of states to underlying local energy minima and the other involves an additional projection to maximally compact conformations. Both methods generate connectivity patterns that allow to distinguish between the good and bad folders. Connectivity graphs corresponding to the folding funnel have few loops and are thus tree-like. The Arrhenius law for the median folding time of a 16-monomer sequence is established and the corresponding barrier is related to easily identifiable kinetic trap states.Comment: REVTeX, 9 pages, 15 EPS figures, to appear in Phys. Rev.