Abstract: Daily and seasonal variations in dry and wet atmospheric nitrogen fluxes have been studied during four campaigns between 2004 and 2006 at a coastal site of the Southern North Sea at De Haan (Belgium) located at coordinates of 51.1723° N and 3.0369° E. Concentrations of inorganic N-compounds were determined in the gaseous phase, size-segregated aerosol (coarse, medium, and fine), and rainwater samples. Dissolved organic nitrogen (DON) was quantified in rainwater. The daily variations in N-fluxes of compounds were evaluated with air-mass backward trajectories, classified into the main air-masses arriving at the sampling site (i.e., continental, North Sea, and Atlantic/UK/Channel). The three, non-episodic campaigns showed broadly consistent fluxes, but during the late summer campaign exceptionally high episodic N-deposition was observed. The average dry and wet fluxes for non-episodic campaigns amounted to 2.6 and 4.0 mg N m−2 d−1, respectively, whereas during the episodic late summer period these fluxes were as high as 5.2 and 6.2 mg N m−2 d−1, respectively. Non-episodic seasons/campaigns experienced average aerosol fluxes of 0.91.4 mg N m−2 d−1. Generally, the contribution of aerosol NH4+ was more significant in the medium and fine particulate fractions than that of aerosol NO3−, whereas the latter contributed more in the coarse fraction, especially in continental air-masses. During the dry mid-summer campaign, the DON contributed considerably (15%) to the total N-budget. Exceptionally high episodic aerosol-N inputs have been observed for the late summer campaign, with especially high deposition rates of 3.6 and 2.9 mg N m−2 d−1 for Atlantic/UK/Channel and North Sea-continental (mixed) air-masses, respectively. During this pollution episode, the flux of NH4+ was dominating in each aerosol fraction/air-mass, except for coarse continental aerosols. High deposition of gaseous-N was also observed in this campaign with an average total N-flux of 22.5-times higher than in other campaigns.

Abstract: Trace elements found in aerosols were monitored in Jerusalem during the 1979 winter season utilizing an X-ray fluoresence technique. Most of the particulate mass was associated with the natural soil elements, such as Ca, Fe, K and Ti. Only a small fraction of the mass was comprised of elements clearly emitted from human sources, e.g. Pb, Br, V, Ni and Zn. An excellent correspondence was found between the enrichment factors observed in this study and those postulated for other parts of the world. However, the concentration of Ca and Sr in the Jerusalem suspended dust is substantially higher when compared with world averages of urban aerosols.

Abstract: Heterogeneous catalysts are often & ldquo;black boxes & rdquo; due to the insufficient understanding of the detailed mechanisms at the catalytic sites. An atomic-level elucidation of the processes taking place in those regions is, thus, mandatory to produce robust and selective heterogeneous catalysts. We have improved the description of the whole reactive scenario for polymeric carbon nitrides (PCN) by combining atomic-level characterizations with magic-angle spinning (MAS) solid-state nuclear magnetic resonance (NMR) spectroscopy, classical reactive molecular dynamics (RMD) simulations, and quantum chemistry (QC) calculations. We disclose the structure & minus;property relationships of an ad hoc modified PCN by inserting an aryl amino group that turned out to be very efficient for the production of H2O2. The main advancement of this work is the development of a difluoromethylene-substituted aryl amino PCN to generate H2O2 at a rate of 2.0 mM & middot;h & minus;1 under the irradiation of household blue LEDs and the identification of possible active catalytic sites with the aid of 15N and 19F MAS solid-state NMR without using any expensive labeling reagent. RMD simulations and QC calculations confirm and further extend the experimental descriptions by revealing the role and locations of the identified functionalities, namely, NH linkers, & minus;NH2 terminal groups, and difluoromethylene units, reactants, and products. <comment>Superscript/Subscript Available</comment

Abstract: A computer routine was developed for qualitative and quantitative analysis of photographically recorded spark-source mass spectra. Particular attention is given to the case of a graphite matrix. The program starts from the line intensities (expressed as Seidel values) and isotope masses calculated from the densitometer readings by a commercially available routine. From the intensities in the different exposures (typically 15 stages), it computes the parameters for the linear parts of the density curves for each ion. Taking into account mutual interferences of multivalent ions, isotope or C-clusters, oxide, carbide and dicarbide ions, the program automatically identifies and then quantifies the elements present. The precision of the results is around 5%. Reading and complete processing of one photoplate is achieved within 23 h.

Abstract: An automated electron microprobe, equipped with an energy-dispersive X-ray spectrometer and an additional backscattered electron signal digitalization system, can allow rapid sizing and major element analysis on numerous particles. A software package has been developed to exploit the particle size and shape information to achieve quantitative analysis of single particles, and to compare the performance of the different matrix correction procedures.

Abstract: A remote site in the Namib Desert was selected for sampling background aerosols in southern Africa, as one of a wide network of stations spanning the Southern Hemisphere in a programme designed to measure the background concentrations of trace elements in the atmosphere. A series of samples was collected over a 6-month period using a single-orifice cascade impactor, which fractionated the particles into six size groups. Analysis was performed using particle-induced X-ray emission (PIXE), yielding results for S, Cl, K, Ca, Ti, Mn, Fe, Br and Sr, and occasionally also for V, Cr, Ni, Cu, Zn and Pb. No direct correlations with wind direction were observed excluding strong local or regional sources of particles. K, Ca, Ti, Mn and Fe can be identified with a dust dispersion source. Cl, large particle S and Br, and part of the K and Sr are derived from sea spray. Relative to the soil components small particle K is not enriched as it normally is in regions with less scarce vegetation. Cr, V, Ni, Cu, Zn and Pb concentrations and enrichments in the aerosol are lower than practically all values measured at any other location hitherto. The concentration of the small particle sulphur, 200 ng m−3, is believed to be related to anaerobic conditions and plankton blooms in the ocean upwelling zones off Namibia.

Abstract: The present paper synthesizes data obtained during a multidisciplinary cruise carried out in June 2004 at the continental margin of the northern Bay of Biscay. The data-set allows to describe the different stages of a coccolithophore bloom dominated by Emiliania huxleyi. The cruise was carried out after the main spring phytoplankton bloom that started in mid-April and peaked in mid-May. Consequently, low phosphate (PO4 < 0.2 μM) and silicate (DSi < 2.0 μM) concentrations, low partial pressure of carbon dioxide (pCO2) and high calcite saturation degree in surface waters combined with thermal stratification, probably favoured the blooming of coccolithophores. During the period of the year our cruise was carried out, internal tides induce enhanced vertical mixing at the continental shelf break leading to the injection of inorganic nutrients to surface waters that probably trigger the bloom. The bloom developed as the water-column stratified and as the water mass was advected over the continental shelf, following the general residual circulation in the area. The most developed phase of the bloom was sampled in a remote sensed high reflectance (HR) patch over the continental shelf that was characterized by low chlorophyll-a (Chl-a) concentration in surface waters (<1.0 μg L−1), high particulate inorganic carbon (PIC) concentration (not, vert, similar8 μmol L−1) and coccolithophore abundance up to 57 × 106 cells L−1. Transparent exopolymer particles (TEP) concentrations ranged between 15 and 75 μg C L−1 and carbon content of TEP represented up to 26% of the particulate organic carbon (POC; maximum concentration of 15.5 μmol L−1 in the upper 40 m). Integrated primary production (PP) ranged between 210 and 680 mg C m−2 d−1 and integrated calcification (CAL) ranged between 14 and 140 mg C m−2 d−1, within the range of PP and CAL values previously reported during coccolithophore blooms in open and shelf waters of the North Atlantic Ocean. Bacterial protein production (BPP) measurements in surface waters (0.30.7 μg C L−1 h−1) were much higher than those reported during early phases of coccolithophore blooms in natural conditions, but similar to those during peak and declining coocolithophorid blooms reported in mesocosms. Total alkalinity anomalies with respect to conservative mixing (ΔTA) down to −49 μmol kg−1 are consistent with the occurrence of biogenic precipitation of calcite, while pCO2 remained 15107 μatm lower than atmospheric equilibrium (372 μatm). The correlation between ΔTA and pCO2 suggested that pCO2 increased in part due to calcification, but this increase was insufficient to overcome the background under-saturation of CO2. This is related to the biogeochemical history of the water masses due to net carbon fixation by the successive phytoplankton blooms in the area prior to the cruise, hence, the investigated area remained a sink for atmospheric CO2 despite calcification.

Abstract: A polynomial approach is applied for a number of data from the Posener-tables to calculate the values of the intensity distribution function of atomic absorption lines – H(a, 0.726a) – at the tabulated damping-parameter values with an error not worse than 0.044 %. For the resultant H(a, 0.726a) data, the ninth and sixth order polynomials can be fitted according to the damping parameter range of 0-2, and 2-10, respectively, which results in a minimal error of approximation. The derived functions are simply applicable to the calculation of any H(a, 0.726a) value belonging to a damping-parameter of any arbitrarily selected spectral line, implying the influence of Doppler- and Lorentz-broadening. The overall error of the described method is lower than 0.4 %.

Abstract: A new method to estimate case specific prediction uncertainty for univariate trilinear partial least squares (tri-PLS1) regression is introduced. This method is, from a theoretical point of view, the most exact finite sample approximation to true prediction uncertainty that has been reported up till now. Using the new method, different error sources can be propagated, which is an advantage that cannot be offered by data driven approaches such as the bootstrap. In a concise example, it is illustrated how the method can be applied. In the Appendix, efficient algorithms are presented to compute the estimates required.