Real-time organic aerosol chemical speciation in the indoor environment using extractive electrospray ionization mass spectrometry

Understanding the sources and composition of organic aerosol (OA) in indoor environments requires rapid measurements, since many emissions and processes have short timescales. However, real-time molecular-level OA measurements have not been reported indoors. Here, we present quantitative measurements, at a time resolution of five seconds, of molecular ions corresponding to diverse aerosol-phase species, by applying extractive electrospray ionization mass spectrometry (EESI-MS) to indoor air analysis for the first time, as part of the highly instrumented HOMEChem field study. We demonstrate how the complex spectra of EESI-MS are screened in order to extract chemical information and investigate the possibility of interference from gas-phase semivolatile species. During experiments that simulated the Thanksgiving US holiday meal preparation, EESI-MS quantified multiple species, including fatty acids, carbohydrates, siloxanes, and phthalates. Intercomparisons with Aerosol Mass Spectrometer (AMS) and Scanning Mobility Particle Sizer suggest that EESI-MS quantified a large fraction of OA. Comparisons with FIGAERO-CIMS shows similar signal levels and good correlation, with a range of 100 for the relative sensitivities. Comparisons with SV-TAG for phthalates and with SV-TAG and AMS for total siloxanes also show strong correlation. EESI-MS observations can be used with gas-phase measurements to identify co-emitted gas- and aerosol-phase species, and this is demonstrated using complementary gas-phase PTR-MS observations.     

Expansion in bioreactors of human progenitor populations from cord blood and mobilized peripheral blood

Umbilical cord blood (UCB) and mobilized peripheral blood (MPB) provide an alternate source to bone marrow for transplantation. Expansion in vitro of stem/progenitor cell populations from these sources may provide adult-sized grafts otherwise not attainable because of the limited cell numbers available in the case of UCB or because of numerous rounds of apheresis required for sufficient MPB cells. We asked whether continuous perfusion culture could be employed in ex vivo expansion to produce clinically relevant numbers of stem/progenitor cells from these sources. To evaluate MPB, 1-10 million leukocytes, from patients who had received either granulocyte colony-stimulating factor (G-CSF) or cyclophosphamide and granulocyte-macrophage colony-stimulating factor (GM-CSF), were inoculated into bioreactors, with or without irradiated, allogeneic stroma. The growth factor combination in the perfusion medium consisted of interleukin-3 (IL-3), stem cell factor (SCF), GM-CSF and erythropoietin (Epo). Under the best conditions tested, total cell numbers, granulocyte-macrophage colony-forming units (CFU-GM), and long-term culture-initiating cell (LTC-IC) populations were expanded by about 50-, 80-, and 20-fold, respectively, over 14 days. At low cell inocula (1 million), the presence of stroma enhanced the expansion of total cells and CFU-GM but not of LTC-IC. When SCF was not included in the medium, both total cells and CFU-GM expanded to a much lesser extent, but again the expansion of LTC-IC was not affected. At the higher cell inoculum (10 million), expansions of total cells and CFU-GM were equivalent with or without stroma. To evaluate UCB, cells were placed into bioreactors with or without irradiated, allogeneic stroma, and the bioreactors were perfused with medium containing the four standard growth factors. After 6-14 days, in several independent experiments, 20-24 million cells were harvested from bioreactors perfused with SCF-containing medium, irrespective of the presence or absence of preformed stroma. Similarly, in reactors perfused with SCF-containing medium (with or without stroma), an average 40- to 60-fold expansion of CFU-GM was obtained, yielding an average of 1.5-1.8 x 10(5) CFU-GM per reactor. Harvested cells were thus up to 40-fold enriched in CFU-GM in comparison to the inoculum. In the absence of SCF, cell expansions averaged 1.5- to 2-fold, and CFU-GM were expanded only 10- to 14-fold by day 14. As before, the presence of preformed stroma did not affect either cell or CFU-GM yields, provided the cell inoculum was at least 4.5 million cells.(ABSTRACT TRUNCATED AT 400 WORDS)     

Automated zebrafish chorion removal and single embryo placement: optimizing throughput of zebrafish developmental toxicity screens

The potential of the developing zebrafish model for toxicology and drug discovery is limited by inefficient approaches to manipulating and chemically exposing zebrafish embryos-namely, manual placement of embryos into 96- or 384-well plates and exposure of embryos while still in the chorion, a barrier of poorly characterized permeability enclosing the developing embryo. We report the automated dechorionation of 1600 embryos at once at 4 h postfertilization (hpf) and placement of the dechorionated embryos into 96-well plates for exposure by 6 hpf. The process removed ≥95% of the embryos from their chorions with 2% embryo mortality by 24 hpf, and 2% of the embryos malformed at 120 hpf. The robotic embryo placement allocated 6-hpf embryos to 94.7% ± 4.2% of the wells in multiple 96-well trials. The rate of embryo mortality was 2.8% (43 of 1536) from robotic handling, the rate of missed wells was 1.2% (18 of 1536), and the frequency of multipicks was <0.1%. Embryo malformations observed at 24 hpf occurred nearly twice as frequently from robotic handling (16 of 864; 1.9%) as from manual pipetting (9 of 864; 1%). There was no statistical difference between the success of performing the embryo placement robotically or manually.     

Limited evidence of zebra mussel (Dreissena polymorpha) consumption by freshwater drum (Aplodinotus grunniens) in Lake Winnipeg

Freshwater drum (Aplodinotus grunniens) may be a predator of the invasive zebra mussel (Dreissena polymorpha), which established in Lake Winnipeg in 2013. In this study, the diets, trophic position, and growth of 51 freshwater drum collected in 2019 (six years post-zebra mussel invasion) were compared to 64 freshwater drum sampled in 2000. Benthic insect larvae were the dominant food items in both years. Although mollusks occur in high densities in Lake Winnipeg, they were only consumed by a few freshwater drum in either sample year. Zebra mussels were not a frequent prey item in 2019 as they were only consumed by four of the sampled freshwater drum. Stable isotope analysis of white muscle tissue yielded similar δ¹³C and δ¹⁵N values in both years and were consistent with a benthic, insectivorous diet. Length-at-age data derived from otoliths revealed that the 2019 population had at least an equal growth rate to the 2000 population. Weight-at-length data suggested that fish condition was greater in 2019 than in 2000, which coincided with increased benthic macroinvertebrate density in Lake Winnipeg. Based on these findings, Lake Winnipeg freshwater drum continue to feed predominantly on insect larvae and not zebra mussels.     

Modeling heavy metal mass releases from urban battery litter

Consumer batteries littered on urban pavements release metals of environmental significance (Ag, Cd, Cr, Cu, Hg, Li, Mn, Ni, Pd, Ti, Zn) to stormwater runoff. Predicting the mass loading of any one metal is difficult because of the random composition of battery litter. However, when littering is modeled as a conditional filtered Poisson process, bounds may be estimated for the mean and variance of site mass loading for any metal if the site litter rate and battery product contributions are known. Site-specific data on the battery brand distribution in litter can improve load estimates, but statistics computed from 5500 littered batteries collected in the Cleveland area may be used to approximate the brand distribution. Zinc load calculations based on battery litter size, type and brand discretizations are implemented in a model titled BLML and illustrated for a case-study location. Results indicate that, at some urban sites, zinc released from battery litter can be the largest source of zinc in urban pavement runoff.     

Toward a human-like biped robot with compliant legs

Conventional models of bipedal walking generally assume rigid body structures, while elastic material properties seem to play an essential role in nature. On the basis of a novel theoretical model of bipedal walking, this paper investigates a model of biped robot which makes use of minimum control and elastic passive joints inspired from the structures of biological systems. The model is evaluated in simulation and a physical robotic platform by analyzing the kinematics and ground reaction force. The experimental results show that, with a proper leg design of passive dynamics and elasticity, an attractor state of human-like walking gait patterns can be achieved through extremely simple control without sensory feedback. The detailed analysis also explains how the dynamic human-like gait can contribute to adaptive biped walking.     

Synthesis and applications of molybdenum (IV) oxide

Molybdenum dioxide (MoO₂) is a transition metal oxide with unusual metal-like electrical conductivity and high catalytic activity toward reforming hydrocarbons. This review covers the synthesis techniques used to fabricate MoO₂ in a variety of morphologies and particle sizes. Processing from molybdenum ore and reduction from MoO₃ are also covered, with emphasis on reduction mechanisms and kinetic considerations. Discussions of various solution-based and gas phase synthesis techniques shed light on strategies to achieve various unique morphologies, which leads into a brief discussion of nanoscale MoO₂. Nanoscale MoO₂ is of interest for important technological applications including catalysts for partial oxidation of hydrocarbons, solid oxide fuel cell anodes, and high-capacity reversible lithium ion battery anodes.     

Characterizing sources and emissions of volatile organic compounds in a northern California residence using space‐ and time‐resolved measurements

We investigate source characteristics and emission dynamics of volatile organic compounds (VOCs) in a single‐family house in California utilizing time‐ and space‐resolved measurements. About 200 VOC signals, corresponding to more than 200 species, were measured during 8 weeks in summer and five in winter. Spatially resolved measurements, along with tracer data, reveal that VOCs in the living space were mainly emitted directly into that space, with minor contributions from the crawlspace, attic, or outdoors. Time‐resolved measurements in the living space exhibited baseline levels far above outdoor levels for most VOCs; many compounds also displayed patterns of intermittent short‐term enhancements (spikes) well above the indoor baseline. Compounds were categorized as “high‐baseline” or “spike‐dominated” based on indoor‐to‐outdoor concentration ratio and indoor mean‐to‐median ratio. Short‐term spikes were associated with occupants and their activities, especially cooking. High‐baseline compounds indicate continuous indoor emissions from building materials and furnishings. Indoor emission rates for high‐baseline species, quantified with 2‐hour resolution, exhibited strong temperature dependence and were affected by air‐change rates. Decomposition of wooden building materials is suggested as a major source for acetic acid, formic acid, and methanol, which together accounted for ~75% of the total continuous indoor emissions of high‐baseline species.     

Indoor emissions of total and fluorescent supermicron particles during HOMEChem

Inhalation of particulate matter is associated with adverse health outcomes. The fluorescent portion of supermicron particulate matter has been used as a proxy for bioaerosols. The sources and emission rates of fluorescent particles in residential environments are not well-understood. Using an ultraviolet aerodynamic particle sizer (UVAPS), emissions of total and fluorescent supermicron particles from common human activities were investigated during the HOMEChem campaign, a test-house investigation of the chemistry of indoor environments. Human occupancy and activities, including cooking and mopping, were found to be considerable sources of indoor supermicron fluorescent particles, which enhanced the indoor particle concentrations by two orders of magnitude above baseline levels. The estimated total (fluorescent) mass emission rates for the activities tested were in the range of 4-30 (1-11) mg per person meal for cooking and 0.1-4.9 (0.05-4.7) mg/h for occupancy and mopping. Model calculations indicate that, once released, the dominant fate of coarse particles (2.5-10 micrometer in diameter) was deposition onto indoor surfaces, allowing for the possibility of subsequent resuspension and consequent exposures over durations much longer than the ventilation time scale. Indoor coarse particle deposition would also contribute to soiling of indoor surfaces.     

Trout‐Skin Gelatin‐Based Edible Films Containing Phenolic Antioxidants: Effect on Physical Properties and Oxidative Stability of Cod‐Liver Oil Model Food

Abstract: Trout‐skin (Oncorhynchus mykiss) gelatin‐based films containing antioxidants (epigallocatechin gallate (EGCG), 50 and 250 ppm w/w) and green tea powder (1% and 20% w/w of gelatin) were tested for tensile strength, elastic modulus, and elongation, and oxygen and water vapor transmission rates, in vitro antioxidant activity using the DPPH (2,2‐diphenyl‐1‐picrylhydrazyl) assay and effect on stabilizing cod‐liver oil held under mild thermal abuse conditions. Cod‐liver oil overlaid with films was stored at 40 °C for 20 d and analyzed for peroxide value (PV) and thiobarbituric acid reactive substances (TBARS). Antioxidant activity was retained in films containing green tea powder, but was reduced (P < 0.05) in EGCG films (20 d, 23 °C). Water vapor transmission rate of the films incorporated with antioxidants did not change significantly (P > 0.05), but the oxygen transmission rate for films with 50 ppm EGCG and 20% green tea powder was significant (P < 0.05). Other physical properties varied with antioxidant incorporation. The TBARS and PV of control oil increased from 0.05 ± 0.01 to 4.71 ± 0.30 g MDA/kg oil and from 3.6 ± 0.2 to 178.3 ± 24.5 millieq peroxides/kg oil, respectively, after 20 d. For cod‐liver oil covered with control or antioxidant‐containing films, TBARS remained below 0.37 g MDA/kg oil and PV below 7 millieq peroxides/kg oil. Incorporation of antioxidants to the films did not reduce oil oxidation (P > 0.05) at the levels tested and this was confirmed by activation energy calculations. The rate of oil oxidation was more dependent upon the inherent oxygen barrier property of the films than the presence of antioxidants. Practical Application: This research has the potential to enhance the utilization of fish skins, a valuable food processing by‐product, as edible films with natural antioxidants to extend the shelf life of foods. The film physical properties and barrier to oxygen and water are investigated.