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The Iterative Closest Point algorithm (ICP) is a standard tool for registration of a source to a target point cloud. In this paper, ICP in point-to-plane mode is adopted to city models that are defined in CityGML. With this new point-to-model version of the algorithm, a coarsely registered photogrammetric point cloud can be matched with buildings' polygons to provide, e.g., a basis for automated 3D facade modeling. In each iteration step, source points are projected to these polygons to find correspondences. Then an optimization problem is solved to find an affine transformation that maps source points to their correspondences as close as possible. Whereas standard ICP variants do not perform scaling, our algorithm is capable of isotropic scaling. This is necessary because photogrammetric point clouds obtained by the structure from motion algorithm typically are scaled randomly. Two test scenarios indicate that the presented algorithm is faster than ICP in point-to-plane mode on sampled city models. [ABSTRACT FROM AUTHOR]

Fine particulate matter (PM) levels and resulting impacts on human health are in the Po Valley (Italy) among the highest in Europe. To build effective PM abatement strategies, it is necessary to characterize fine PM chemical composition, sources and atmospheric processes on long time scales (> months), with short time resolution (< day), and with particular emphasis on the predominant organic fraction. Although previous studies have been conducted in this region, none of them addressed all these aspects together. For the first time in the Po Valley, we investigate the chemical composition of non-refractory submicron PM (NR-PM1) with a time-resolution of 30 minutes at the regional background site of Ispra during one full year, using an Aerosol Chemical Speciation Monitor (ACSM) under the most up-to-date and stringent quality assurance protocol. The identification of the main components of the organic fraction is made using the Multilinear-Engine 2 algorithm implemented within the latest version of the SoFi toolkit. In addition, with a view of a potential implementation of ACSM measurements in European air quality networks as a replacement of traditional filter-based techniques, parallel multiple off-line analyses were carried out to assess the performance of the ACSM in the determination of PM chemical species regulated by Air Quality Directives. The annual NR-PM1 level monitored at the study site (14.2 µg/m³) is among the highest in Europe, and is even comparable to levels reported in urban areas like New York City (USA, 14.2 µg/m³) and Tokyo (Japan, 12-15 µg/m³). On the annual basis, submicron particles are primarily composed of organic aerosol (OA, 58% of NR-PM1). This fraction was apportioned into oxygenated OA (OOA, 66%), hydrocarbon-like OA (HOA, 11% of OA), and biomass burning OA (BBOA, 23%). Among the primary sources of OA, biomass burning (23%) is thus bigger than fossil fuel combustion (11%). Significant contributions of aged secondary organic aerosol (OOA) are observed throughout the year. The unexpectedly high degree of oxygenation estimated during wintertime is probably due to the contribution of secondary BBOA and the enhancement of aqueous phase production of OOA during cold months. BBOA and nitrate are the only components of which contributions increase with the NR-PM1 levels. Therefore, biomass burning and NOx emission reductions would be particularly efficient in limiting submicron aerosol pollution events. Abatement strategies conducted during cold seasons appear to be more efficient than annual-based policies. In a broader context, further studies using high-time resolution analytical techniques on a long-term basis for the characterization of fine aerosol should help better shape our future air quality policies, which constantly need refinement. [ABSTRACT FROM AUTHOR]

As part of the European ACTRIS project, the first large Quadrupole Aerosol Chemical Speciation Monitor (Q-ACSM) intercomparison study was conducted in the region of Paris for 3 weeks during the late-fall -- early-winter period (November-December 2013). The first week was dedicated to the tuning and calibration of each instrument, whereas the second and third were dedicated to side-by-side comparison in ambient conditions with co-located instruments providing independent information on submicron aerosol optical, physical, and chemical properties. Near real-time measurements of the major chemical species (organic matter, sulfate, nitrate, ammonium, and chloride) in the non-refractory submicron aerosols (NR-PM 1) were obtained here from 13 Q-ACSM. The results show that these instruments can produce highly comparable and robust measurements of the NR-PM 1 total mass and its major components. Taking the median of the 13 Q-ACSM as a reference for this study, strong correlations (r² > 0.9) were observed systematically for each individual Q-ACSM across all chemical families except for chloride for which three Q-ACSMs showing weak correlations partly due to the very low concentrations during the study. Reproducibility expanded uncertainties of Q-ACSM concentration measurements were determined using appropriate methodologies defined by the International Standard Organization (ISO 17025, 1999) and were found to be 9, 15, 19, 28, and 36% for NR-PM 1, nitrate, organic matter, sulfate, and ammonium, respectively. However, discrepancies were observed in the relative concentrations of the constituent mass fragments for each chemical component. In particular, significant differences were observed for the organic fragment at mass-to-charge ratio 44, which is a key parameter describing the oxidation state of organic aerosol. Following this first major intercomparison exercise of a large number of Q-ACSMs, detailed intercomparison results are presented, along with a discussion of some recommendations about best calibration practices, standardized data processing, and data treatment. [ABSTRACT FROM AUTHOR]

In early spring the Baltic region is frequently affected by high pollution events due to biomass burning in that area. Here we present a comprehensive study to investigate the impact of biomass/grass burning (BB) on the evolution and composition of aerosol in Preila, Lithuania, during springtime open fires. Non-refractory submicron particulate matter (NR-PM1) was measured by an Aerodyne aerosol chemical speciation monitor (ACSM) and a source apportionment with the multilinear engine (ME-2) running the positive matrix factorization (PMF) model was applied to the organic aerosol fraction to investigate the impact of biomass/grass burning. Satellite observations over regions of biomass burning activity supported the results and identification of air mass transport to the area of investigation. Sharp increases in biomass burning tracers, such as levoglucosan up to 683 ng m-3 and black carbon (BC) up to 17 μg m-3 were observed during this period. A further separation between fossil and non-fossil primary and secondary contributions was obtained by coupling ACSM PMF results and radiocarbon (14C) measurements of the elemental (EC) and organic (OC) carbon fractions. Non-fossil organic carbon (OCnf) was the dominant fraction of PM1, with the primary (POCnf) and secondary (SOCnf) fractions contributing 26-44 % and 13-23 % to the TC, respectively. 5-8 % of the TC had a primary fossil origin (POCf), whereas the contribution of fossil secondary organic carbon (SOCf) was 4-13 %. Non-fossil EC (ECnf) and fossil EC (ECf) ranged from 13-24 % and 7-12 %, respectively. Isotope ratio of stable carbon and nitrogen isotopes were used to distinguish aerosol particles associated with solid and liquid fossil fuel burning. [ABSTRACT FROM AUTHOR]

Chemically resolved (organic, nitrate, sulphate, ammonium) data of non-refractory sub-micron (NR-PM1) aerosol from the first long-term deployment (27 July 2012 to 02 October 2013) of a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) at the Swiss high altitude site Jungfraujoch (3580 m a.s.l.) are presented. Besides total mass loadings, diurnal variations and relative species contributions during the different meteorological seasons, geographical origin and sources of organic aerosol (OA) are discussed. Backward transport simulations shows that the highest (especially sulphate) concentrations of NR-PM1 were measured in air masses advected to the station from regions south of the JFJ while lowest concentrations were seen from western regions. OA source apportionment for each season was performed using the Source Finder (SoFi) interface for the multilinear engine (ME-2). OA was dominated in all seasons by oxygenated OA (OOA, 71-88%), with lesser contributions from local tourism-related activities (7-12%) and hydrocarbon-like OA related to regional vertical transport (3-9%). In summer the OOA can be separated into a background low-volatility OA (LV-OOA I, possibly associated with long range transport) and a slightly less oxidised low-volatility OA (LV-OOA II) associated with regional vertical transport. Wood burning-related OA associated with regional transport was detected during the whole winter 2012/2013 and during rare events in summer 2013, in the latter case attributed to small scale transport for the surrounding valleys. Additionally, the data were divided into periods with free tropospheric (FT) conditions and periods with planetary boundary layer (PBL) influence enabling the assessment of the composition for each. Most nitrate and part of the OA is injected from the regional PBL while sulphate is mainly produced in the FT. The south/north gradient of sulphate is also pronounced in FT air masses (sulphate mass fraction from the south: 45%, from the north: 29%). Furthermore, a detailed investigation of specific marker fragments of the OA spectra (f43, f44, f55, f57, f60) showed different degrees of ageing depending on season. [ABSTRACT FROM AUTHOR]

Chemically resolved atmospheric aerosol data sets from the largest intercomparison of the Aerodyne aerosol chemical speciation monitors (ACSMs) performed to date were collected at the French atmospheric supersite SIRTA. In total 13 quadrupole ACSMs (Q-ACSM) from the European ACTRIS ACSM network, one time-of-flight ACSM (ToF-ACSM), and one high-resolution ToF aerosol mass spectrometer (AMS) were operated in parallel for about 3 weeks in November and December 2013. Part 1 of this study reports on the accuracy and precision of the instruments for all the measured species. In this work we report on the intercomparison of organic components and the results from factor analysis source apportionment by positive matrix factorisation (PMF) utilising the multilinear engine 2 (ME-2). Except for the organic contribution of mass-to-charge ratio m/z 44 to the total organics (f44), which varied by factors between 0.6 and 1.3 compared to the mean, the peaks in the organic mass spectra were similar among instruments. The m/z 44 differences in the spectra resulted in a variable f44 in the source profiles extracted by ME-2, but had only a minor influence on the extracted mass contributions of the sources. The presented source apportionment yielded four factors for all 15 instruments: hydrocarbon-like organic aerosol (HOA), cooking-related organic aerosol (COA), biomass burning-related organic aerosol (BBOA) and secondary oxygenated organic aerosol (OOA). ME-2 boundary conditions (profile constraints) were optimised individually by means of correlation to external data in order to achieve equivalent / comparable solutions for all ACSM instruments and the results are discussed together with the investigation of the influence of alternative anchors (reference profiles). A comparison of the ME-2 source apportionment output of all 15 instruments resulted in relative standard deviations (SD) from the mean between 13.7 and 22.7% of the source's average mass contribution depending on the factors (HOA: 14.3 º 2.2 %, COA: 15.0 º 3.4 %, OOA: 41.5 º 5.7 %, BBOA: 29.3 º 5.0 %). Factors which tend to be subject to minor factor mixing (in this case COA) have higher relative uncertainties than factors which are recognised more readily like the OOA. Averaged over all factors and instruments the relative first SD from the mean of a source extracted with ME-2 was 17.2 %. [ABSTRACT FROM AUTHOR]

The terpenols L(-)-borneol, (1S2S3S5R)-3-pinanol, (-)-menthol, and (-)-myrtenol are easily available chiral alcohols for the preparation of enantiomerically pure catechol esters 1-4-H2. Those ligands are used for the hierarchical assembly of triple lithium-bridged dinuclear titanium(IV) triscatecholate helicates Li[Li3(1-4)6Ti2]. In solution, the dimeric species are in a solvent dependent equilibrium with the monomer Li2[(1-4)3Ti]. The equilibrium is studied by ¹H NMR. CD spectroscopy indicates that the configuration at the complex units of the enantiomerically pure dimeric α-chiral derivatives Li[Li3(1-3)6Ti2] is opposite to the configuration of the monomers Li2[(1-3)3Ti]. For the γ-chiral complex Li2[(4)3Ti] only a de of 25% is observed and in this case no interpretation of the mechanism of stereocontrol is possible. [ABSTRACT FROM AUTHOR]

We present a new instrument for monitoring aerosol composition, the time-of-flight aerosol chemical speciation monitor (ToF-ACSM), combining precision state-ofthe- art time-of-flight mass spectrometry with stability, reliability, and easy handling, which are necessities for long-term monitoring operations on the scale of months to years. Based on Aerodyne aerosol mass spectrometer (AMS) technology, the ToF-ACSM provides continuous online measurements of chemical composition and mass of non-refractory submicron aerosol particles. In contrast to the larger AMS, the compactsized and lower-priced ToF-ACSM does not feature particle sizing, similar to the widely-used quadrupole-ACSM (QACSM). Compared to the Q-ACSM, the ToF-ACSM features a better mass resolution of M/ΔM = 600 and better detection limits on the order of <30 ngm-3 for a time resolution of 30 min. With simple upgrades these limits can be brought down by another factor of ∼8. This allows for operation at higher time resolutions and in low concentration environments. The associated software packages (single packages for integrated operation and calibration and analysis) provide a high degree of automation and remote access, minimising the need for trained personnel on site. Intercomparisons with Q-ACSM, C-ToF-AMS, nephelometer and scanning mobility particle sizer (SMPS) measurements, performed during a first long-term deployment (>10 months) on the Jungfraujoch mountain ridge (3580ma.s.l.) in the Swiss Alps, agree quantitatively. Additionally, the mass resolution of the ToFACSM is sufficient for basic mass defect resolved peak fitting of the recorded spectra, providing a data stream not accessible to the Q-ACSM. This allows for quantification of certain hydrocarbon and oxygenated fragments (e.g. C3H+ 7 and C2H3O+, both occurring at m/Q= 43 Th), as well as improving inorganic/organic separation. [ABSTRACT FROM AUTHOR]

The stable singlet carbenes N,N ′-bis(2,2-dimethylpropyl)-benzimidazolin-2-ylidene 1 and 1,3,4,5-tetramethylimidazol-2-ylidene 2 react with phosphaalkynes P≡C-- t Bu ( 3a ) or P≡C--N i Pr 2 ( 3b ) regioselective to give the aromatic 1,2,4-triphosphole derivatives ( 1 or 2 + 3a → 6a or 6b , respectively) or 1,2,3-triphosphetene ( 1 + 3b → 7 ) or azaphospholene ( 2 + 3b → 9 ) in almost quantitative yields. The mechanisms of the surprising formation of compound 9 under C--H-activation was studied by quantum chemical DFT calculations. [ABSTRACT FROM AUTHOR]

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