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.     

Synthesis and characterization of a pyrochlore solid solution in the Na2O-Bi2O3-TiO2 system

The compositional limits of a previously reported (J. Am. Ceram. Soc., 61, 5-8. (1978)) but relatively unstudied sodium-bismuth titanate pyrochlore solid solution are revised and their electrical properties presented. The pyrochlore solid solution we report forms via a different mechanism to that originally reported and occurs in a different location within the Na₂O-Bi₂O₃-TiO₂ ternary system. In both cases, relatively large amounts of vacancies are required on the A-sites and on the oxygen sites, similar to that reported for undoped ‘Bi₂Ti₂O₇’ pyrochlore. In contrast to ‘Bi₂Ti₂O₇’, this ternary pyrochlore solid solution can be prepared and ceramics sintered using conventional solid-state methods; however, the processing requires several challenges to be overcome to obtain dense ceramics. This cubic pyrochlore series has low electrical conductivity (and does not exhibit any evidence of oxide-ion conduction) and exhibits relaxor ferroelectric behavior with a broad permittivity maximum of ~100 near room temperature. Variable temperature neutron diffraction data do not provide any conclusive evidence for a phase transition in the pyrochlore solid solution between ~4 and 873 K.     

Finite element modeling of resistive surface layers by micro-contact impedance spectroscopy

Micro-contact impedance spectroscopy (MCIS) is potentially a powerful tool for the exploration of resistive surface layers on top of a conductive bulk or substrate material. MCIS employs micro-contacts in contrast to conventional IS where macroscopic electrodes are used. To extract the conductivity of each region accurately using MCIS requires the data to be corrected for geometry. Using finite element modeling on a system where the resistivity of the surface layer is at least a factor of ten greater than the bulk/substrate, we show how current flows through the two layers using two typical micro-contact configurations. This allows us to establish if and what is the most accurate and reliable method for extracting conductivity values for both regions. For a top circular micro-contact and a full bottom counter electrode, the surface layer conductivity (σ_s) can be accurately extracted using a spreading resistance equation if the thickness is ~10 times the micro-contact radius; however, bulk conductivity (σ_b) values can not be accurately determined. If the contact radius is 10 times the thickness of the resistive surface, a geometrical factor using the micro-contact area provides accurate σ_s values. In this case, a spreading resistance equation also provides a good approximation for σ_b. For two top circular micro-contacts on thin resistive surface layers, the MCIS response from the surface layer is independent of the contact separation; however, the bulk response is dependent on the contact separation and at small separations contact interference occurs. As a consequence, there is not a single ideal experimental setup that works; to obtain accurate σ_s and σ_b values the micro-contact radius, surface layer thickness and the contact separation must all be considered together. Here we provide scenarios where accurate σ_s and σ_b values can be obtained that highlight the importance of experimental design and where appropriate equations can be employed for thin and thick resistive surface layers.     

Response of isotopically tailored titanium diboride to neutron irradiation

The response of polycrystalline TiB₂ to neutron irradiation was investigated. The material was fabricated using isotopically enriched ¹¹B powders to minimize helium production via the ¹⁰B(n, α)⁷Li reaction. Neutron irradiation was conducted at temperatures of ~200°C and ~600°C to a fast fluence of 2.4 × 10²⁵ n/m² (>0.1 MeV). The material exhibited some swelling, but less swelling at the higher irradiation temperature. No macroscopic damage was observed in the irradiated material, although moderate irradiation-induced micro-cracking was found in the irradiated TiB₂. This study demonstrated improved radiation resistance of isotopically tailored TiB₂ compared with natural boron TiB₂, which exhibited macroscopic fracture by irradiation.     

Conversion of natural gas jet flame burners to hydrogen

In a study of conversion from CH₄ to H₂, jet flame characteristics of these gases and their blends are compared on a burner diameter scale of mm. Low velocity H₂ and CH₄ jets, burned on pipes of different diameters, indicate higher blow-off limits for H₂, but lower heat release rates, a consequence of its lower specific energy. Compensation for this might be obtained through increased H₂ flow velocity, or a small increase in pipe diameter. Blended CH₄/H₂ flames have lower heat release rates than CH₄ alone, yet small proportions of H_2, with CH₄ might still be burned, on a CH₄ burner. Throughout, fundamental understanding is enhanced through two dimensionless groups: laminar flame thickness normalised by burner diameter, δ_k/D, and the dimensionless flow number, U1. These suggest an optimal role for H₂ combustion, utilizing its high acoustic and blow-off velocities, in high intensity, subsonic, combustors, at low δ_k/D, and high U1.     

Bioelectronic protein nanowire sensors for ammonia detection

Electronic sensors based on biomaterials can lead to novel green technologies that are low cost, renewable, and eco-friendly. Here we demonstrate bioelectronic ammonia sensors made from protein nanowires harvested from the microorganism Geobacter sulfurreducens. The nanowire sensor responds to a broad range of ammonia concentrations (10 to 10⁶ ppb), which covers the range relevant for industrial, environmental, and biomedical applications. The sensor also demonstrates high selectivity to ammonia compared to moisture and other common gases found in human breath. These results provide a proof-of-concept demonstration for developing protein nanowire based gas sensors for applications in industry, agriculture, environmental monitoring, and healthcare.

     

Associations between management practices and within-pen prevalence of calf diarrhea and respiratory disease on dairy farms using automated milk feeders

Data on management practices used with automated milk feeders (AMF) are needed to identify factors associated with calf health in these systems. The objectives of this observational, longitudinal, cross-sectional study were to estimate the prevalence of calf diarrhea (CD) and bovine respiratory disease (BRD), and to identify factors associated with prevalence of these diseases at the pen level on dairy farms feeding milk to group-housed calves with AMF. Seventeen dairy farms with AMF in Ontario, Canada, were visited 4 times, seasonally, over 1 yr. The clinical health of all calves (n = 1,488) in pens (n = 35) with AMF was scored to identify the number of calves with CD and BRD. Data on calf, feeder, and pen management practices were analyzed using generalized linear mixed regression models for each disease. Overall calf-level prevalence of CD and BRD were 23 and 17%, respectively. Median (interquartile range, IQR) within-pen prevalence of CD and BRD were 17% (7 to 37%) and 11% (0 to 28%), respectively. Median age (IQR) for diarrheic calves was 25 d (16 to 42 d), and for calves with BRD was 43 d (29 to 60 d). Factors associated with lower within-pen prevalence of CD were the administration of vitamin E and selenium at birth [odds ratio (OR) = 0.56; 95% confidence interval (CI): 0.32 to 0.99], feeding of probiotics (OR = 0.44, 95% CI: 0.22 to 0.93), and adding fresh bedding every 2 to 3 d (OR = 0.43; 95% CI: 0.24 to 0.76) compared with every 7 or more days. In contrast, sharing air with older cattle (>9 mo old) was associated with increased within-pen prevalence of CD (OR = 4.54, 95% CI: 1.88 to 10.52). Additionally, total bacteria counts ≥100,000 cfu/mL in milk samples taken from the AMF mixing jar were associated with increased within-pen prevalence of CD during the summer visit (OR = 3.34; 95% CI: 1.31 to 8.54). Increased total solids in milk or milk replacer (OR = 0.48, 95% CI: 0.27 to 0.85) and feeding whole milk versus milk replacer (OR = 0.29, 95% CI: 0.11 to 0.75) were associated with lower within-pen prevalence of BRD. Factors associated with greater within-pen prevalence of BRD were sharing air with weaned cattle up to 8 mo old (OR = 3.21, 95% CI: 1.26 to 8.16), and greater depth of the wet bedding pack. The use of maternity pens for reasons other than just calving was associated with increased prevalence of both CD and BRD (OR = 1.85, 95% CI: 1.03 to 3.33; OR = 2.61, 95% CI: 1.21 to 5.58, respectively). These results suggest that isolation from older animals and frequent cleaning of the feeder and pen may help to reduce disease prevalence in group-housed calves fed with an AMF.     

A Pilot Study of the VirtuSphere as a Virtual Reality Enhancement

This pilot study assessed the utility and acceptability of the VirtuSphere, a cutting edge navigation platform designed to enhance presence in virtual environments. The VirtuSphere includes a 12-ft hollow sphere within which the user stands, and it rolls within a wheeled platform, in any direction, according to the user's steps. The pilot was a within-subject crossover design comparing the VirtuSphere to standard game controller navigation. The comparison was based on locomotion in Virtual Iraq, a virtual world resembling Iraqi war zones. Participants were 10 active duty soldiers not suffering from posttraumatic stress disorder. Results indicated that there were negligible differences in sense of presence, simulator sickness, and satisfaction across the two navigation systems. Although the VirtuSphere may provide entertainment value, these results do not provide initial support for the use of the VirtuSphere to improve constructs thought to be important to behavioral health applications of virtual reality. Potential improvements to the design of the VirtuSphere are discussed.     

Changes in Tissue Lipid and Fatty Acid Composition of Farmed Rainbow Trout in Response to Dietary Camelina Oil as a Replacement of Fish Oil

Camelina oil (CO) replaced 50 and 100 % of fish oil (FO) in diets for farmed rainbow trout (initial weight 44 ± 3 g fish^?1). The oilseed is particularly unique due to its high lipid content (40 %) and high amount of 18:3n‐3 (α‐linolenic acid, ALA) (30 %). Replacing 100 % of fish oil with camelina oil did not negatively affect growth of rainbow trout after a 12‐week feeding trial (FO = 168 ± 32 g fish^?1; CO = 184 ± 35 g fish^?1). Lipid and fatty acid profiles of muscle, viscera and skin were significantly affected by the addition of CO after 12 weeks of feeding. However, final 22:6n‐3 [docosahexaenoic acid (DHA)] and 20:5n‐3 [eicosapentaenoic acid (EPA)] amounts (563 mg) in a 75 g fillet (1 serving) were enough to satisfy daily DHA and EPA requirements (250 mg) set by the World Health Organization. Other health benefits include lower SFA and higher MUFA in filets fed CO versus FO. Compound‐specific stable isotope analysis (CSIA) confirmed that the δ¹³C isotopic signature of DHA in CO fed trout shifted significantly compared to DHA in FO fed trout. The shift in DHA δ¹³C indicates mixing of a terrestrial isotopic signature compared to the isotopic signature of DHA in fish oil‐fed tissue. These results suggest that ~27 % of DHA was synthesized from the terrestrial and isotopically lighter ALA in the CO diet rather than incorporation of DHA from fish meal in the CO diet. This was the first study to use CSIA in a feeding experiment to demonstrate synthesis of DHA in fish.