Phosphorus (P) is an indispensable element for all life on Earth and, during the past decade, concerns about the future of its global supply have stimulated much research on soil P and method development. This review provides an overview of advanced state‐of‐the‐art methods currently used in soil P research. These involve bulk and spatially resolved spectroscopic and spectrometric P speciation methods (1 and 2D NMR, IR, Raman, Q‐TOF MS/MS, high resolution‐MS, NanoSIMS, XRF, XPS, (µ)XAS) as well as methods for assessing soil P reactions (sorption isotherms, quantum‐chemical modeling, microbial biomass P, enzymes activity, DGT, ³³P isotopic exchange, ¹⁸O isotope ratios). Required experimental set‐ups and the potentials and limitations of individual methods present a guide for the selection of most suitable methods or combinations.

Ship engine emissions are important with regard to lung and cardiovascular diseases especially in coastal regions worldwide. Known cellular responses to combustion particles include oxidative stress and inflammatory signalling. To provide a molecular link between the chemical and physical characteristics of ship emission particles and the cellular responses they elicit and to identify potentially harmful fractions in shipping emission aerosols. Through an air-liquid interface exposure system, we exposed human lung cells under realistic in vitro conditions to exhaust fumes from a ship engine running on either common heavy fuel oil (HFO) or cleaner-burning diesel fuel (DF). Advanced chemical analyses of the exhaust aerosols were combined with transcriptional, proteomic and metabolomic profiling including isotope labelling methods to characterise the lung cell responses. The HFO emissions contained high concentrations of toxic compounds such as metals and polycyclic aromatic hydrocarbon, and were higher in particle mass. These compounds were lower in DF emissions, which in turn had higher concentrations of elemental carbon (“soot”). Common cellular reactions included cellular stress responses and endocytosis. Reactions to HFO emissions were dominated by oxidative stress and inflammatory responses, whereas DF emissions induced generally a broader biological response than HFO emissions and affected essential cellular pathways such as energy metabolism, protein synthesis, and chromatin modification. Despite a lower content of known toxic compounds, combustion particles from the clean shipping fuel DF influenced several essential pathways of lung cell metabolism more strongly than particles from the unrefined fuel HFO. This might be attributable to a higher soot content in DF. Thus the role of diesel soot, which is a known carcinogen in acute air pollution-induced health effects should be further investigated. For the use of HFO and DF we recommend a reduction of carbonaceous soot in the ship emissions by implementation of filtration devices.

Heavy petroleum fractions such as vacuum gas oils (VGOs) are structurally and compositionally highly complex mixtures. Nitrogen species, which have a significant impact on the subsequent refining processes, are generally removed by the hydrodenitrogenation (HDN) catalytic process. The purpose of this study was to identify and characterize compounds that are refractory to the HDN process. This may allow for the examination of the effectiveness of a vacuum distillate hydrotreatment catalytic bed in removing nitrogen-containing compounds before the cracking step. Three different VGO fractions of the same oil before and after HDN processes were analysed in ESI(+) mode by FTICR mass spectrometry and ion mobility spectrometry–mass spectrometry (IMS-MS), in particular compounds containing basic nitrogen, such as quinoline and isoquinoline. Ultra-high-resolution FTICR mass spectrometry provides a sufficiently high mass resolution power to resolve different compounds and attribute a unique molecular formula to each ion. Information on the isomeric content was obtained by use of tandem mass spectrometry (MS/MS) and IMS-MS. The evolution of the fragmentation of the N₁ class of compounds as a function of collision energy allowed for the identification of the molecular nucleus raw formula. From the IMS-MS experiments, it clearly appeared that, based on the IMS peak width, a lower isomeric dispersity was obtained after the HDN process and, based on the drift time and collision cross section determination, species presenting longer alkyl branches are the molecules most refractory to the HDN process.