Detection and Sizing of Ti-Containing Particles in Recreational Waters Using Single Particle ICP-MS.

Single particle inductively coupled plasma mass spectrometry (spICP-MS) was used to detect Ti-containing particles in heavily-used bathing areas of a river (Salt River) and five swimming pools. Ti-containing particle concentrations in swimming pools ranged from 2.8 × 103 to 4.4 × 103 particles/mL and were an order of magnitude lower than those detected in the Salt River. Measurements from the Salt River showed an 80% increase in Ti-containing particle concentration over baseline concentration during peak recreational activity (at 16:00 h) in the river. Cloud point extraction followed by transmission electron microscopy with energy dispersive X-ray analysis confirmed presence of aggregated TiO2 particles in river samples, showing morphological similarity to particles present in an over-the-counter sunscreen product. The maximum particle mass concentration detected in a sample from the Salt River (659 ng/L) is only slightly lower than the predicted no effect concentration for TiO2 to aquatic organisms (< 1 µg/L).

Potential Environmental Impacts and Antimicrobial Efficacy of Silver- and Nanosilver-Containing Textiles.

For textiles containing nanosilver, we assessed benefit (antimicrobial efficacy) in parallel with potential to release nanosilver (impact) during multiple life cycle stages. The silver loading and method of silver attachment to the textile highly influenced the silver release during washing. Multiple sequential simulated household washing experiments for fabric swatches in deionized water with or without detergent showed a range of silver release. The toxicity of washing experiment supernatants to zebrafish (Danio rerio) embryos was negligible, with the exception of the very highest Ag releases (∼1 mg/L Ag). In fact, toxicity tests indicated that residual detergent exhibited greater adverse response than the released silver. Although washing the fabrics did release silver, it did not affect their antimicrobial efficacy, as demonstrated by >99.9% inhibition of E. coli growth on the textiles, even for textiles that retained as little as 2 µg/g Ag after washing. This suggests that very little nanosilver is required to control bacterial growth in textiles. Visible light irradiation of the fabrics reduced the extent of Ag release for textiles during subsequent washings. End-of-life experiments using simulated landfill conditions showed that silver remaining on the textile is likely to continue leaching from textiles after disposal in a landfill.

Release of TiO2 nanoparticles from sunscreens into surface waters: a one-year survey at the old Danube recreational Lake.

Monitoring data are necessary for the future production of engineered nanomaterials and the development of regulations for nanomaterials. Therefore, it is necessary to develop methods that reliably detect and quantify nanomaterials in real-world systems at expectedly low concentrations. In this work we tested several methodological approaches to detect titanium dioxide nanomaterials released from sunscreen products into the Old Danube Lake (Vienna, Austria), which is heavily used for recreational activities like bathing and water sports during the summer season. During a 12-month period suspended particulate matter (SPM) was collected from the lake and analyzed using a combination of complementary techniques. By sampling at a location approximately 50 m from the nearest bathing area and at one meter depth from the water surface, we focused on the potentially mobile fraction of the released nanoparticles. We were able to identify titanium dioxide nanoparticles stemming from sunscreens in the suspended matter of the lake using electron microscopy. Bulk analysis of SPM clearly shows an increase of Ti-containing particles during the summer season. These analyses, however, are not able to distinguish sunscreen nanoparticles from natural Ti-bearing nanoparticles. Therefore, Elemental ratios of Ti with Al, V, Ga, Y, Nb, Eu, Ho, Er, Tm, Yb, and Ta as determined by ICPMS and ICPOES, in combination with single particle ICPMS analysis were applied to establish local background values. The observed mild increase of Ti elemental ratios, compared to spring background values indicates that the residence time of released nanomaterials in the water column is rather short. Overall, the advantages and disadvantages of the methods used to detect and characterize the nanomaterials are discussed.

Nanoparticle size detection limits by single particle ICP-MS for 40 elements.

The quantification and characterization of natural, engineered, and incidental nano- to micro-size particles are beneficial to assessing a nanomaterial's performance in manufacturing, their fate and transport in the environment, and their potential risk to human health. Single particle inductively coupled plasma mass spectrometry (spICP-MS) can sensitively quantify the amount and size distribution of metallic nanoparticles suspended in aqueous matrices. To accurately obtain the nanoparticle size distribution, it is critical to have knowledge of the size detection limit (denoted as Dmin) using spICP-MS for a wide range of elements (other than a few available assessed ones) that have been or will be synthesized into engineered nanoparticles. Herein is described a method to estimate the size detection limit using spICP-MS and then apply it to nanoparticles composed of 40 different elements. The calculated Dmin values correspond well for a few of the elements with their detectable sizes that are available in the literature. Assuming each nanoparticle sample is composed of one element, Dmin values vary substantially among the 40 elements: Ta, U, Ir, Rh, Th, Ce, and Hf showed the lowest Dmin values, ≤10 nm; Bi, W, In, Pb, Pt, Ag, Au, Tl, Pd, Y, Ru, Cd, and Sb had Dmin in the range of 11-20 nm; Dmin values of Co, Sr, Sn, Zr, Ba, Te, Mo, Ni, V, Cu, Cr, Mg, Zn, Fe, Al, Li, and Ti were located at 21-80 nm; and Se, Ca, and Si showed high Dmin values, greater than 200 nm. A range of parameters that influence the Dmin, such as instrument sensitivity, nanoparticle density, and background noise, is demonstrated. It is observed that, when the background noise is low, the instrument sensitivity and nanoparticle density dominate the Dmin significantly. Approaches for reducing the Dmin, e.g., collision cell technology (CCT) and analyte isotope selection, are also discussed. To validate the Dmin estimation approach, size distributions for three engineered nanoparticle samples were obtained using spICP-MS. The use of this methodology confirms that the observed minimum detectable sizes are consistent with the calculated Dmin values. Overall, this work identifies the elements and nanoparticles to which current spICP-MS approaches can be applied, in order to enable quantification of very small nanoparticles at low concentrations in aqueous media.

Clearing and staining small vertebrates for demonstrating ossification of the skeletal system using the KOH and glycerine clearing method.

Preparing articulated skeletons of small vertebrates is extremely difficult due to the presence of vast amounts of cartilage and/or the extremely small size of skeletal components. Clearing the tissues surrounding small skeletons and staining the bones in toto reveals the skeletal system without the risk of displacing the bony components. The specimens are first fixed and bleached which renders the tissues preserved and transparent. These specimens may then be exposed to alizarin red S which stains bone a pink to red colour making them visible through the transparent soft tissues. Toluidine blue may also be used to stain cartilage a blue colour. The Spalteholz staining method is cited, though the focus will be on the KOH and glycerine clearing method for macroscopic observation.

Relative skeletal distribution of proliferating marrow in the adult dog determined using 3'-deoxy-3'-[18 F]fluorothymidine.

3'-deoxy-3'-[18 F]fluorothymidine (18 FLT) is a radiopharmaceutical tracer used with positron emission tomography (PET), often in combination with computed tomography (CT), to image DNA synthesis, and thus, cellular proliferation. Characteristic accumulation of the tracer within haematopoietic bone marrow provides a noninvasive means to assess marrow activity and distribution throughout the living animal. The present study utilizes three-dimensional analysis of 18 FLT-PET/CT scans to quantify the relative skeletal distribution of active marrow by anatomic site in the dog. Scans were performed on six healthy, adult (3-6 years of age), mixed-breed dogs using a commercially available PET/CT scanner consisting of a 64-slice helical CT scanner combined with an integrated four ring, high-resolution LSO PET scanner. Regions of interest encompassing 11 separate skeletal regions (skull, cervical vertebral column, thoracic vertebral column, lumbar vertebral column, sacrum, ribs, sternum, scapulae, proximal humeri, ossa coxarum, and proximal femora) were manually drawn based on CT images and thresholded by standardized uptake value to delineate bone marrow activity. Activity within each skeletal region was then divided by the total skeletal activity to derive the per cent of overall marrow activity within an individual site. The majority of proliferative marrow was located within the vertebral column. Of the sites traditionally accessed clinically for marrow sampling, the proximal humerus contained the largest percentage, followed by the ossa coxarum, proximal femur, and sternum, respectively. This information may be used to guide selection of traditional marrow sampling sites as well as inform efforts to spare important sites of haematopoiesis in radiation therapy planning.

Linear statistical model for growth in stature from birth to maturity.

A model for the physical growth of individual children from birth to adulthood is proposed which is linear in the model parameters. The advantages of linear over nonlinear models include the relative ease and costs of fitting the model to data of individuals and the fact that statistical methods are more readily available for analysis of parameters from linear models than for nonlinear models. The proposed linear model and the non-linear triple logistic model are both fit to the measured lengths of two boys and two girl followed from birth to 18 years of age.

Correlation of computed tomographic images with anatomic features of the abdomen of ringed seals (Phoca hispida).

OBJECTIVE: To correlate anatomic features of the abdomen of the ringed seal (Phoca hispida) identified in plastinated cross-sections with images obtained via computed tomography (CT) and thereby establish reference standards for normal abdominal organ size and position in this species. SAMPLE POPULATION: 2 adult male ringed seal cadavers. PROCEDURE: With the seal in sternal recumbency, CT images of the abdomen were acquired by use of a 4th-generation CT scanner. Image slice thickness was 1 cm, with no interslice gap. After imaging, the abdominal region was sectioned transversely into 4-cm slices, which were plastinated and photographed. Plastinated slices were matched to their corresponding CT images in preparation for anatomic descriptions. RESULTS: Relevant anatomic features were identified and labeled on both the plastinated tissue slice and corresponding CT image. Normal abdominal organ size and position were assessed, and topographic relationships among organs were ascertained. CONCLUSIONS AND CLINICAL RELEVANCE: The data obtained provide some reference standards for normal abdominal organ size and position in ringed seals. This information may aid researchers of future physiologic and clinical studies in this species.

Detection of single walled carbon nanotubes by monitoring embedded metals.

Detection of single walled carbon nanotubes (CNTs) was performed using single particle-inductively coupled plasma-mass spectrometry (spICPMS). Due to the ambiguities inherent in detecting CNTs by carbon analysis, particularly in complex environmental matrices, this study focuses on using trace catalytic metals intercalated in the CNT structure as proxies for the nanotubes. Using a suite of commercially available CNTs, the monoisotopic elements Co and Y were found to be the most effective for differentiation of particulate pulses from background. The small, variable, amount of trace metal in each CNT makes separation from instrumental background challenging; multiple cut-offs for determining CNT number concentration were investigated to maximize the number of CNTs detected and minimize the number of false positives in the blanks. In simple solutions the number of CNT pulses detected increased linearly with concentration in the ng L−1 range. However, analysis of split samples by both spICPMS and Nanoparticle Tracking Analysis (NTA) showed the quantification of particle number concentration by spICPMS to be several orders of magnitude lower than by NTA. We postulate that this is a consequence of metal content and/or size, caused by the presence of many CNTs that do not contain enough metal to be above the instrument detection limit, resulting in undercounting CNTs by spICPMS. However, since the detection of CNTs at low ng L−1 concentrations is not possible by other techniques, spICPMS is still a more sensitive technique for detecting the presence of CNTs in environmental, materials, or biological applications. To highlight the potential of spICPMS in environmental studies the release of CNTs from polymer nanocomposites into solution was monitored, showcasing the technique's ability to detect changes in released CNT concentrations as a function of CNT loading.

Silver nanowire exposure results in internalization and toxicity to Daphnia magna.

Nanowires (NWs), high-aspect-ratio nanomaterials, are increasingly used in technological materials and consumer products and may have toxicological characteristics distinct from nanoparticles. We carried out a comprehensive evaluation of the physicochemical stability of four silver nanowires (AgNWs) of two sizes and coatings and their toxicity to Daphnia magna . Inorganic aluminum-doped silica coatings were less effective than organic poly(vinyl pyrrolidone) coatings at preventing silver oxidation or Ag(+) release and underwent a significant morphological transformation within 1 h following addition to low ionic strength Daphnia growth media. All AgNWs were highly toxic to D. magna but less toxic than ionic silver. Toxicity varied as a function of AgNW dimension, coating, and solution chemistry. Ag(+) release in the media could not account for observed AgNW toxicity. Single-particle inductively coupled plasma mass spectrometry distinguished and quantified dissolved and nanoparticulate silver in microliter-scale volumes of Daphnia magna hemolymph with a limit of detection of approximately 10 ppb. The silver levels within the hemolymph of Daphnia exposed to both Ag(+) and AgNW met or exceeded the initial concentration in the growth medium, indicating effective accumulation during filter feeding. Silver-rich particles were the predominant form of silver in hemolymph following exposure to both AgNWs and Ag(+). Scanning electron microscopy imaging of dried hemolymph found both AgNWs and silver precipitates that were not present in the AgNW stock or the growth medium. Both organic and inorganic coatings on the AgNW were transformed during ingestion or absorption. Pathway, gene ontology, and clustering analyses of gene expression response indicated effects of AgNWs distinct from ionic silver on Daphnia magna .

Solubility of nano-zinc oxide in environmentally and biologically important matrices.

Increasing manufacture and use of engineered nanoparticles is leading to a greater probability for release of engineered nanoparticles into the environment and exposure to organisms. In particular, zinc oxide (ZnO) is toxic, although it is unclear whether this toxicity is due to the zinc oxide nanoparticles, dissolution to Zn(2+) , or some combination thereof. The goal of this study was to determine the relative solubilities of both commercially available and in-house synthesized ZnO in matrices used for environmental fate and transport or biological toxicity studies. Dissolution of ZnO was observed in nanopure water (7.18-7.40 mg/L dissolved Zn, as measured by filtration) and Roswell Park Memorial Institute medium (RPMI-1640) (∼5 mg/L), but much more dissolution was observed in Dulbecco's modified Eagle's medium, in which the dissolved Zn concentration exceeded 34 mg/L. Moderately hard water exhibited low Zn solubility, likely because of precipitation of a Zn carbonate solid phase. Precipitation of a Zn-containing solid phase in RPMI also appeared to limit Zn solubility. Equilibrium conditions with respect to ZnO solubility were not apparent in these matrices, even after more than 1,000 h of dissolution. These results suggest that solution chemistry exerts a strong influence on ZnO dissolution and can result in limits on Zn solubility from precipitation of less soluble solid phases.

Macroscopic anatomy of the reproductive tract of the reproductively quiescent female emu (Dromaius novaehollandiae).

Three reproductively quiescent female emus (Dromaius novaehollandiae) were embalmed with 10% formalin solution. The reproductive tract was dissected and described. The reproductive tract consists of an ovary and oviduct situated on the left side of the abdominal cavity. The left ovary is dark brown to black in colour with follicles covering the ventral surface. The ovary is located medial to the spleen and closely associated with the ventral surface of the cranial and middle lobes of the left kidney. The oviduct is a relatively straight tube that extends from the level of the cranial extent of the left ilium to the caudal border of the left pubic bone. The oviduct is grossly divided into the infundibulum, magnum, isthmus, uterus and vagina using variations in the mucosal fold pattern.