A compact and portable deposition chamber to study nanoparticles in air-exposed tissue

BACKGROUND Epidemiological studies show that elevated levels of particulate matter in ambient air are highly correlated with respiratory and cardiovascular diseases. Atmospheric particles originate from a large number of sources and have a highly complex and variable composition. An assessment of their potential health risks and the identification of the most toxic particle sources would require a large number of investigations. Due to ethical and economic reasons, it is desirable to reduce the number of in vivo studies and to develop suitable in vitro systems for the investigation of cell-particle interactions. METHODS We present the design of a new particle deposition chamber in which aerosol particles are deposited onto cell cultures out of a continuous air flow. The chamber allows for a simultaneous exposure of 12 cell cultures. RESULTS Physiological conditions within the deposition chamber can be sustained constantly at 36-37°C and 90-95% relative humidity. Particle deposition within the chamber and especially on the cell cultures was determined in detail, showing that during a deposition time of 2 hr 8.4% (24% relative standard deviation) of particles with a mean diameter of 50 nm [mass median diameter of 100 nm (geometric standard deviation 1.7)] are deposited on the cell cultures, which is equal to 24-34% of all charged particles. The average well-to-well variability of particles deposited simultaneously in the 12 cell cultures during an experiment is 15.6% (24.7% relative standard deviation). CONCLUSIONS This particle deposition chamber is a new in vitro system to investigate realistic cell-particle interactions at physiological conditions, minimizing stress on the cell cultures other than from deposited particles. A detailed knowledge of particle deposition characteristics on the cell cultures allows evaluating reliable dose-response relationships. The compact and portable design of the deposition chamber allows for measurements at any particle sources of interest.

Study of the radioactivity induced in air by a 15-MeV proton beam.

Radioactivity induced by a 15-MeV proton beam extracted into air was studied at the beam transport line of the 18-MeV cyclotron at the Bern University Hospital (Inselspital). The produced radioactivity was calculated and measured by means of proportional counters located at the main exhaust of the laboratory. These devices were designed for precise assessment of air contamination for radiation protection purposes. The main produced isotopes were 11C, 13N and 14O. Both measurements and calculations correspond to two different irradiation conditions. In the former, protons were allowed to travel for their full range in air. In the latter, they were stopped at the distance of 1.5 m by a beam dump. Radioactivity was measured continuously in the exhausted air starting from 2 min after the end of irradiation. For this reason, the short-lived 14O isotope gave a negligible contribution to the measured activity. Good agreement was found between the measurements and the calculations within the estimated uncertainties. Currents in the range of 120–370 nA were extracted in air for 10–30 s producing activities of 9–22 MBq of 11C and 13N. The total activities for 11C and 13N per beam current and irradiation time for the former and the latter irradiation conditions were measured to be (3.60 ± 0.48) × 10−3 MBq (nA s)−1 and (2.89 ± 0.37) × 10−3 MBq (nA s)−1, respectively.

Confirmation analysis of ethyl glucuronide and ethyl sulfate in human serum and urine by CZE-ESI-MS(n) after intake of alcoholic beverages

CZE coupled to sheath liquid-based electrospray ionization (ESI) and multiple-stage ion trap mass spectrometry (MS(n) ) was used for the confirmation analysis of ethyl glucuronide (EtG) and ethyl sulfate (EtS) in human serum and urine collected after intake of alcoholic beverages. Electrophoretic separations were performed in uncoated fused-silica capillaries using a pH 9.5 ammonium acetate background electrolyte and normal polarity. MS detection of EtG and EtS occurred after negative ionization using a spray liquid containing 0.5% v/v ammonia in isopropanol/water (60:40%, v/v). CZE-MS and CZE-MS² results obtained after injection of solid-phase extracts for EtG and EtS and of diluted urine confirmed the presence of EtG and EtS in samples whose levels were previously determined by CZE with indirect UV detection. Detection limits of each compound were estimated to be around 2.0 (injection of diluted urine) and 0.2 μg/mL (extracts).

PBDEs in the atmosphere over the Asian marginal seas, and the Indian and Atlantic oceans

Air samples were collected from Jan 16 to Mar 14, 2008 onboard the Oceanic II- The Scholar Ship which navigated an east–west transect from Shanghai to Cape Verde, and polybrominated diphenyl ethers (PBDEs) were analyzed in these samples. PBDE concentrations in the atmosphere over the open seas were influenced by proximity to source areas and land, and air mass origins. The concentrations of Σ21PBDEs over the East and South China Seas, the Bay of Bengal and the Andaman Sea, the Indian Ocean, and the Atlantic Ocean were 10.8 ± 6.13, 3.22 ± 1.57, 5.12 ± 3.56, and 2.87 ± 1.81 pg m−3, respectively. BDE-47 and -99 were the dominant congeners in all the samples, suggesting that the widely used commercial penta-BDE products were the original sources. Over some parts of Atlantic and Indian Ocean, daytime concentrations of BDE-47 and BDE-99 were higher than the concentrations at night. The strong atmospheric variability does not always coincide with a diurnal cycle, but the variability in air concentrations in such remote areas of the ocean remains strong. No significant trends were found for each of PBDE congener with latitude.

Gasoline emissions dominate over diesel in formation of secondary organic aerosol mass

Although laboratory experiments have shown that organic compounds in both gasoline fuel and diesel engine exhaust can form secondary organic aerosol (SOA), the fractional contribution from gasoline and diesel exhaust emissions to ambient SOA in urban environments is poorly known. Here we use airborne and ground-based measurements of organic aerosol (OA) in the Los Angeles (LA) Basin, California made during May and June 2010 to assess the amount of SOA formed from diesel emissions. Diesel emissions in the LA Basin vary between weekdays and weekends, with 54% lower diesel emissions on weekends. Despite this difference in source contributions, in air masses with similar degrees of photochemical processing, formation of OA is the same on weekends and weekdays, within the measurement uncertainties. This result indicates that the contribution from diesel emissions to SOA formation is zero within our uncertainties. Therefore, substantial reductions of SOA mass on local to global scales will be achieved by reducing gasoline vehicle emissions.

GATS and the Regulation of Trade in Services

This collection of essays takes stock of the key challenges that have arisen since the entry into force of the General Agreement on Trade in Services in the mid-1990s and situates them in the context of the WTO's Doha Development Agenda and the proliferation of preferential agreements addressing services today. The multidisciplinary approach provides an opportunity for many of the world's leading experts and a number of new analytical voices to exchange ideas on the future of services trade and regulation. Cosmopolitan approaches to the treatment of labour mobility, the shape of services trade disciplines in the digital age and pro-competitive regulation in air transport are explored with a view to helping readers gain a better understanding of the forces shaping the changes. An essential read for all those concerned with the evolution of the rules-based trading system and its impact on the service economy.

Ultrasonic acoustic emissions in drought-stressed trees - more than signals from cavitation?

Ultrasonic acoustic emission (UAE) in trees is often related to collapsing water columns in the flow path as a result of tensions that are too strong (cavitation). However, in a decibel (dB) range below that associated with cavitation, a close relationship was found between UAE intensities and stem radius changes. • UAE was continuously recorded on the stems of mature field-grown trees of Scots pine (Pinus sylvestris) and pubescent oak (Quercus pubescens) at a dry inner-Alpine site in Switzerland over two seasons. The averaged 20-Hz records were related to microclimatic conditions in air and soil, sap-flow rates and stem-radius fluctuations de-trended for growth (ΔW). • Within a low-dB range (27 ± 1 dB), UAE regularly increased and decreased in a diurnal rhythm in parallel with ΔW on cloudy days and at night. These low-dB emissions were interrupted by UAE abruptly switching between the low-dB range and a high-dB range (36 ± 1 dB) on clear, sunny days, corresponding to the widely supported interpretation of UAE as sound from cavitations. • It is hypothesized that the low-dB signals in drought-stressed trees are caused by respiration and/or cambial growth as these physiological activities are tissue water-content dependent and have been shown to produce courses of CO2 efflux similar to our courses of ΔW and low-dB UAE.

Nano Aerosol Chamber for In-Vitro Toxicity (NACIVT) studies.

Abstract Inhalation of ambient air particles or engineered nanoparticles (NP) handled as powders, dispersions or sprays in industrial processes and contained in consumer products pose a potential and largely unknown risk for incidental exposure. For efficient, economical and ethically sound evaluation of health hazards by inhaled nanomaterials, animal-free and realistic in vitro test systems are desirable. The new Nano Aerosol Chamber for in-vitro Toxicity studies (NACIVT) has been developed and fully characterized regarding its performance. NACIVT features a computer-controlled temperature and humidity conditioning, preventing cellular stress during exposure and allowing long-term exposures. Airborne NP are deposited out of a continuous air stream simultaneously on up to 24 cell cultures on Transwell® inserts, allowing high-throughput screening. In NACIVT, polystyrene as well as silver particles were deposited uniformly and efficiently on all 24 Transwell® inserts. Particle-cell interaction studies confirmed that deposited particles reach the cell surface and can be taken up by cells. As demonstrated in control experiments, there was no evidence for any adverse effects on human bronchial epithelial cells (BEAS-2B) due to the exposure treatment in NACIVT. The new, fully integrated and transportable deposition chamber NACIVT provides a promising tool for reliable, acute and sub-acute dose-response studies of (nano)particles in air-exposed tissues cultured at the air-liquid interface.

Patterns and controls of sediment production, transfer and yield in the Illgraben

Quantification of the volumes of sediment removed by rock–slope failure and debris flows and identification of their coupling and controls are pertinent to understanding mountain basin sediment yield and landscape evolution. This study captures a multi-decadal period of hillslope erosion and channel change following an extreme rock avalanche in 1961 in the Illgraben, a catchment prone to debris flows in the Swiss Alps. We analyzed photogrammetrically-derived datasets of hillslope and channel erosion and deposition along with climatic and seismic variables for a 43 year period from 1963 to 2005. Based on these analyses we identify and discuss (1) patterns of hillslope production, channel transfer and catchment sediment yield, (2) their dominant interactions with climatic and seismic variables, and (3) the nature of hillslope–channel coupling and implications for sediment yield and landscape evolution in this mountain basin. Our results show an increase in the mean hillslope erosion rate in the 1980s from 0.24 ± 0.01 m yr− 1 to 0.42 ± 0.03 m yr− 1 that coincided with a significant increase in air temperature and decrease in snow cover depth and duration, which we presume led to an increase in the exposure of the slopes to thermal weathering processes. The combination of highly fractured slopes close to the threshold angle for failure, and multiple potential triggering mechanisms, means that it is difficult to identify an individual control on slope failure. On the other hand, the rate of channel change was strongly related to variables influencing runoff. A period of particularly high channel erosion rate of 0.74 ± 0.02 m yr− 1 (1992–1998) coincided with an increase in the frequency and magnitude of intense rainfall events. Hillslope erosion exceeded channel erosion on average, indicative of a downslope-directed coupling relationship between hillslope and channel, and demonstrating the first order control of rock–slope failure on catchment sediment yield and landscape evolution.

Glacial–interglacial dynamics of Antarctic firn columns: comparison between simulations and ice core air-δ15N measurements

Correct estimation of the firn lock-in depth is essential for correctly linking gas and ice chronologies in ice core studies. Here, two approaches to constrain the firn depth evolution in Antarctica are presented over the last deglaciation: outputs of a firn densification model, and measurements of δ15N of N2 in air trapped in ice core, assuming that δ15N is only affected by gravitational fractionation in the firn column. Since the firn densification process is largely governed by surface temperature and accumulation rate, we have investigated four ice cores drilled in coastal (Berkner Island, BI, and James Ross Island, JRI) and semi-coastal (TALDICE and EPICA Dronning Maud Land, EDML) Antarctic regions. Combined with available ice core air-δ15N measurements from the EPICA Dome C (EDC) site, the studied regions encompass a large range of surface accumulation rates and temperature conditions. Our δ15N profiles reveal a heterogeneous response of the firn structure to glacial–interglacial climatic changes. While firn densification simulations correctly predict TALDICE δ15N variations, they systematically fail to capture the large millennial-scale δ15N variations measured at BI and the δ15N glacial levels measured at JRI and EDML – a mismatch previously reported for central East Antarctic ice cores. New constraints of the EDML gas–ice depth offset during the Laschamp event (~41 ka) and the last deglaciation do not favour the hypothesis of a large convective zone within the firn as the explanation of the glacial firn model–δ15N data mismatch for this site. While we could not conduct an in-depth study of the influence of impurities in snow for firnification from the existing datasets, our detailed comparison between the δ15N profiles and firn model simulations under different temperature and accumulation rate scenarios suggests that the role of accumulation rate may have been underestimated in the current description of firnification models.

Can the carbon isotopic composition of methane be reconstructed from multi-site firn air measurements?

Methane is a strong greenhouse gas and large uncertainties exist concerning the future evolution of its atmospheric abundance. Analyzing methane atmospheric mixing and stable isotope ratios in air trapped in polar ice sheets helps in reconstructing the evolution of its sources and sinks in the past. This is important to improve predictions of atmospheric CH4 mixing ratios in the future under the influence of a changing climate. The aim of this study is to assess whether past atmospheric δ13C(CH4) variations can be reliably reconstructed from firn air measurements. Isotope reconstructions obtained with a state of the art firn model from different individual sites show unexpectedly large discrepancies and are mutually inconsistent. We show that small changes in the diffusivity profiles at individual sites lead to strong differences in the firn fractionation, which can explain a large part of these discrepancies. Using slightly modified diffusivities for some sites, and neglecting samples for which the firn fractionation signals are strongest, a combined multi-site inversion can be performed, which returns an isotope reconstruction that is consistent with firn data. However, the isotope trends are lower than what has been concluded from Southern Hemisphere (SH) archived air samples and high-accumulation ice core data. We conclude that with the current datasets and understanding of firn air transport, a high precision reconstruction of δ13C of CH4 from firn air samples is not possible, because reconstructed atmospheric trends over the last 50 yr of 0.3–1.5 ‰ are of the same magnitude as inherent uncertainties in the method, which are the firn fractionation correction (up to ~2 ‰ at individual sites), the Kr isobaric interference (up to ~0.8 ‰, system dependent), inter-laboratory calibration offsets (~0.2 ‰) and uncertainties in past CH4 levels (~0.5 ‰).

Lake surface temperatures in a changing climate: a global sensitivity analysis

We estimate the effects of climatic changes, as predicted by six climate models, on lake surface temperatures on a global scale, using the lake surface equilibrium temperature as a proxy. We evaluate interactions between different forcing variables, the sensitivity of lake surface temperatures to these variables, as well as differences between climate zones. Lake surface equilibrium temperatures are predicted to increase by 70 to 85 % of the increase in air temperatures. On average, air temperature is the main driver for changes in lake surface temperatures, and its effect is reduced by ~10 % by changes in other meteorological variables. However, the contribution of these other variables to the variance is ~40 % of that of air temperature, and their effects can be important at specific locations. The warming increases the importance of longwave radiation and evaporation for the lake surface heat balance compared to shortwave radiation and convective heat fluxes. We discuss the consequences of our findings for the design and evaluation of different types of studies on climate change effects on lakes.

High secondary aerosol contribution to particulate pollution during haze events in China

Rapid industrialization and urbanization in developing countries has led to an increase in air pollution, along a similar trajectory to that previously experienced by the developed nations. In China, particulate pollution is a serious environmental problem that is influencing air quality, regional and global climates, and human health. In response to the extremely severe and persistent haze pollution experienced by about 800 million people during the first quarter of 2013 (refs 4, 5), the Chinese State Council announced its aim to reduce concentrations of PM2.5 (particulate matter with an aerodynamic diameter less than 2.5micrometres) by up to 25 per cent relative to 2012 levels by 2017 (ref. 6). Such efforts however require elucidation of the factors governing the abundance and composition of PM2.5, which remain poorly constrained in China. Here we combine a comprehensive set of novel and state-of-the-art offline analytical approaches and statistical techniques to investigate the chemical nature and sources of particulate matter at urban locations in Beijing, Shanghai, Guangzhou and Xi'an during January 2013. We find that the severe haze pollution event was driven to a large extent by secondary aerosol formation, which contributed 30-77 per cent and 44-71 per cent (average for all four cities) of PM2.5 and of organic aerosol, respectively. On average, the contribution of secondary organic aerosol (SOA) and secondary inorganic aerosol (SIA) are found to be of similar importance (SOA/SIA ratios range from 0.6 to 1.4). Our results suggest that, in addition to mitigating primary particulate emissions, reducing the emissions of secondary aerosol precursors from, for example, fossil fuel combustion and biomass burning is likely to be important for controlling China's PM2.5 levels and for reducing the environmental, economic and health impacts resulting from particulate pollution.

The Synthesis of Functionalised Diaryltetraynes and Their Transport Properties in Single-Molecule Junctions

The synthesis and characterisation is described of six diaryltetrayne derivatives [Ar-(C[TRIPLE BOND]C)4-Ar] with Ar=4-NO2-C6H4- (NO24), 4-NH(Me)C6H4- (NHMe4), 4-NMe2C6H4- (NMe24), 4-NH2-(2,6-dimethyl)C6H4- (DMeNH24), 5-indolyl (IN4) and 5-benzothienyl (BTh4). X-ray molecular structures are reported for NO24, NHMe4, DMeNH24, IN4 and BTh4. The stability of the tetraynes has been assessed under ambient laboratory conditions (20 °C, daylight and in air): NO24 and BTh4 are stable for at least six months without observable decomposition, whereas NHMe4, NMe24, DMeNH24 and IN4 decompose within a few hours or days. The derivative DMeNH24, with ortho-methyl groups partially shielding the tetrayne backbone, is considerably more stable than the parent compound with Ar=4-NH2C6H4 (NH24). The ability of the stable tetraynes to anchor in Au|molecule|Au junctions is reported. Scanning-tunnelling-microscopy break junction (STM-BJ) and mechanically controllable break junction (MCBJ) techniques are employed to investigate single-molecule conductance characteristics.

Breakdown voltage of metal-oxide resistors in liquid argon

We characterized a sample of metal-oxide resistors and measured their breakdown voltage in liquid argon by applying high voltage (HV) pulses over a 3 second period. This test mimics the situation in a HV-divider chain when a breakdown occurs and the voltage across resistors rapidly rise from the static value to much higher values. All resistors had higher breakdown voltages in liquid argon than their vendor ratings in air at room temperature. Failure modes range from full destruction to coating damage. In cases where breakdown was not catastrophic, subsequent breakdown voltages were lower in subsequent measuring runs. One resistor type withstands 131 kV pulses, the limit of the test setup.