Top-down approaches to measure total integrated emissions provide verification of bottom-up, temporally resolved, inventory-based estimations. Aircraft-based measurements of air pollutants from sources in the Canadian oil sands were made in support of the Joint Canada-Alberta Implementation Plan for Oil Sands Monitoring during a summer intensive field campaign between 13 August and 7 September 2013. The measurements contribute to knowledge needed in support of the Joint Canada-Alberta Implementation Plan for Oil Sands Monitoring. This paper describes the top-down emission rate retrieval algorithm (TERRA) to determine facility emissions of pollutants, using SO2 and CH4 as examples, based on the aircraft measurements. In this algorithm, the flight path around a facility at multiple heights is mapped to a two-dimensional vertical screen surrounding the facility. The total transport of SO2 and CH4 through this screen is calculated using aircraft wind measurements, and facility emissions are then calculated based on the divergence theorem with estimations of box-top losses, horizontal and vertical turbulent fluxes, surface deposition, and apparent losses due to air densification and chemical reaction. Example calculations for two separate flights are presented. During an upset condition of SO2 emissions on one day, these calculations are within 5% of the industry-reported, bottom-up measurements. During a return to normal operating conditions, the SO2 emissions are within 11% of industry-reported, bottom-up measurements. CH4 emissions calculated with the algorithm are relatively constant within the range of uncertainties. Uncertainty of the emission rates is estimated as less than 30 %, which is primarily due to the unknown SO2 and CH4 mixing ratios near the surface below the lowest flight level.
In high performance perovskite based solar cells, CH3NH3PbI3 is the key material. We carried out a study on charge diffusion in spin-coated CH3NH3PbI3 perovskite thin film by transient fluorescent spectroscopy. A thickness-dependent fluorescent lifetime was found. By coating the film with an electron or hole transfer layer, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) or 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (Spiro-OMeTAD) respectively, we observed the charge transfer directly through the fluorescence quenching. One-dimensional diffusion model was applied to obtain long charge diffusion distances in thick films, which is ~1.7 mum for electrons and up to ~6.3 mum for holes. Short diffusion distance of few hundreds of nanosecond was also observed in thin films. This thickness dependent charge diffusion explained the formerly reported short charge diffusion distance (~100 nm) in films and resolved its confliction to thick working layer (300-500 nm) in real devices. This study presents direct support to the high performance perovskite solar cells and will benefit the devices' design.
In high performance perovskite based solar cells, CH3NH3PbI3 is the key material. We carried out a study on charge diffusion in spin-coated CH3NH3PbI3 perovskite thin film by transient fluorescent spectroscopy. A thickness-dependent fluorescent lifetime was found. By coating the film with an electron or hole transfer layer, [6,6]-phenyl-C-61-butyric acid methyl ester (PCBM) or 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (Spiro-OMeTAD) respectively, we observed the charge transfer directly through the fluorescence quenching. One-dimensional diffusion model was applied to obtain long charge diffusion distances in thick films, which is similar to 1.7 mu m for electrons and up to similar to 6.3 mu m for holes. Short diffusion distance of few hundreds of nanosecond was also observed in thin films. This thickness dependent charge diffusion explained the formerly reported short charge diffusion distance (similar to 100 nm) in films and resolved its confliction to thick working layer (300-500 nm) in real devices. This study presents direct support to the high performance perovskite solar cells and will benefit the devices' design.
Proton transfer through hydrogen bonds plays a fundamental role in many physical, chemical and biological processes. Proton dynamics is susceptible to quantum tunnelling, which typically involves many hydrogen bonds simultaneously, leading to correlated many-body tunnelling. In contrast to the well-studied incoherent single-particle tunnelling, our understanding of many-body tunnelling is still in its infancy. Here we report the real-space observation of concerted proton tunnelling in a cyclic water tetramer using a cryogenic scanning tunnelling microscope. This is achieved by monitoring the reversible interconversion of the hydrogen-bonding chirality of the water tetramer with a chlorine-terminated scanning tunnelling microscope tip. We found that the presence of the Cl anion at the tip apex may either enhance or suppress the concerted tunnelling process, depending on the details of the coupling symmetry between the Cl ion and the protons. Our work opens up the possibility of controlling the quantum states of protons with atomic-scale precision.
We fabricate carbon nanotube (CNT)-field effect transistors (FETs) with a changeable channel length and investigate the electron transport properties of single-walled, double-walled and triple-walled CNTs under uniaxial strain. In particular, we characterize the atomic structure of the same CNTs in the devices by transmission electron microscopy and correlate the strain-induced electronic property change to the chirality of the CNTs. Both the off-state resistance and on-state resistance are observed to change with the axial strain following an exponential function. The strain-induced band gap change obtained from the maximum resistance change in the transfer curve of the ambipolar FETs is quantitatively compared with the previous theoretical prediction and our DFTB calculation from the chirality of the CNTs. Although following the same trend, the experimentally obtained strain-induced band gap change is obviously larger (57%-170% larger) than the theoretical results for all the six CNTs, indicating that more work is needed to fully understand the strain-induced electronic property change of CNTs.
Ammonia oxidation is known to be performed by both ammonia-oxidizing archaea (AOA) and bacteria (AOB), although their relative significance to nitrification process in soil ecosystems remains controversial. The distribution of AOA and AOB in plateau soils with different land use types and the influential factors remains unclear. The present study investigated the abundance and structure of AOA and AOB communities in upland soils adjacent to Erhai Lake in the Yunnan Plateau (China). Quantitative PCR assays indicated a large variation in the community size of AOA and AOB communities, with the numerical dominance of AOA over AOB in most of soils. Clone library analysis illustrated a marked shift in the structure of soil AOA and AOB communities. A high abundance of Nitrososphaera- and Nitrosotalea-like AOA was observed, while Nitrosospira-like species predominated in AOB. AOA and AOB abundance was positively influenced by total nitrogen and moisture content, respectively. Moreover, moisture content might be a key determinant of AOA community composition, while C/N and nitrate nitrogen played an important role in shaping AOB community composition. However, further efforts will be necessary in order to elucidate the links between soil AOA and AOB and land use.
Both ammonia-oxidizing bacteria (AOB) and archaea (AOA) can play important roles in ammonia biotransformation in ecosystems. However, the factors regulating the distribution of these microorganisms in lacustrine ecosystems remain essentially unclear. The present study investigated the effects of geographic location on the distribution of sediment AOA and AOB in 13 freshwater lakes on the Yunnan Plateau (China). The spatial dissimilarity in the abundance and structure of sediment AOA and AOB communities was observed in these plateau lakes. AOA abundance was usually less than AOB abundance, and the AOA/AOB ratio was positively correlated with water depth. Nitrososphaera-like AOA occurred in most of the studied lakes and were dominant in two lakes. Nitrosospira was the dominant AOB species in most of the lakes, while Nitrosomonas showed high abundance only in three lakes. In addition, geographic location was found to affect lake sediment AOB community structure.
Both Bacteria and Archaea might be involved in various biogeochemical processes in lacustrine sediment ecosystems. However, the factors governing the intra-lake distribution of sediment bacterial and archaeal communities in various freshwater lakes remain unclear. The present study investigated the sediment bacterial and archaeal communities in 13 freshwater lakes on the Yunnan Plateau. Quantitative PCR assay showed a large variation in bacterial and archaeal abundances. Illumina MiSeq sequencing illustrated high bacterial and archaeal diversities. Bacterial abundance was regulated by sediment total organic carbon and total nitrogen, and water depth, while nitrate nitrogen was an important determinant of bacterial diversity. Proteobacteria, Acidobacteria, Actinobacteria, Bacteroidetes, Chlorobi, Chloroflexi, Cyanobacteria, Firmicutes, Gemmatimonadetes, Nitrospirae, Planctomycetes, and Verrucomicrobia were the major components of sediment bacterial communities. Proteobacteria was the largest phylum, but its major classes and their proportions varied greatly among different lakes, affected by sediment nitrate nitrogen. In addition, both Euryarchaeota and Crenarchaeota were important members in sediment archaeal communities, while unclassified Archaea usually showed the dominance.
Active smoking is a major preventable public health problem and an established critical factor for epigenetic modification. In this systematic review, we identified 17 studies addressing the association of active smoking exposure with methylation modifications in blood DNA, including 14 recent epigenome-wide association studies (EWASs) and 3 gene-specific methylation studies (GSMSs) on the gene regions identified by EWASs. Overall, 1460 smoking-associated CpG sites were identified in the EWASs, of which 62 sites were detected in multiple (>/=3) studies. The three most frequently reported CpG sites (genes) in whole blood samples were cg05575921 (AHRR), cg03636183 (F2RL3), and cg19859270 (GPR15), followed by other loci within intergenic regions 2q37.1 and 6p21.33. These significant smoking-related genes were further assessed by specific methylation assays in three GSMSs and reflected not only current but also lifetime or long-term exposure to active smoking. In conclusion, this review summarizes the evidences for the use of blood DNA methylation patterns as biomarkers of smoking exposure for research and clinical practice. In particular, it provides a reservoir for constructing a smoking exposure index score which could be used to more precisely quantify long-term smoking exposure and evaluate the risks of smoking-induced diseases.