Identification and source attribution of organic compounds in ultrafine particles near Frankfurt International Airport

Analysing the composition of ambient ultrafine particles (UFPs) is a challenging task due to the low mass and chemical complexity of small particles, yet it is a prerequisite for the identification of particle sources and the assessment of potential health risks. Here, we show the molecular characterization of UFPs, based on cascade impactor (Nano-MOUDI) samples that were collected at an air quality monitoring station near one of Europe's largest airports, in Frankfurt, Germany. At this station, particle-size-distribution measurements show an enhanced number concentration of particles smaller than 50 nm during airport operating hours. We sampled the lower UFP fraction (0.010–0.018, 0.018–0.032, 0.032–0.056 µm) when the air masses arrived from the airport. We developed an optimized filter extraction procedure using ultra-high-performance liquid chromatography (UHPLC) for compound separation and a heated electrospray ionization (HESI) source with an Orbitrap high-resolution mass spectrometer (HRMS) as a detector for organic compounds. A non-target screening detected ∼200 organic compounds in the UFP fraction with sample-to-blank ratios larger than 5. We identified the largest signals as homologous series of pentaerythritol esters (PEEs) and trimethylolpropane esters (TMPEs), which are base stocks of aircraft lubrication oils. We unambiguously attribute the majority of detected compounds to jet engine lubrication oils by matching retention times, high-resolution and accurate mass measurements, and comparing tandem mass spectrometry (MS2) fragmentation patterns between both ambient samples and commercially available jet oils. For each UFP stage, we created molecular fingerprints to visualize the complex chemical composition of the organic fraction and their average carbon oxidation state. These graphs underline the presence of the homologous series of PEEs and TMPEs and the appearance of jet oil additives (e.g. tricresyl phosphate, TCP). Targeted screening of TCP confirmed the absence of the harmful tri-ortho isomer, while we identified a thermal transformation product of TMPE-based lubrication oil (trimethylolpropane phosphate, TMP-P). Even though a quantitative determination of the identified compounds is limited, the presented method enables the qualitative detection of molecular markers for jet engine lubricants in UFPs and thus strongly improves the source apportionment of UFPs near airports.

Qualitative and Quantitative Characterization of Airport-related Ultrafine Particles using Liquid Chromatography – High-Resolution Mass Spectrometry (UHPLC/HRMS)

<p>We present the results from a chemical characterization study of ultrafine particles (UFP), collected nearby Frankfurt International Airport where particle size distribution measurements showed high number concentrations for particles with a diameter <50 nm. Aluminium filter samples were collected at an air quality monitoring station in a distance of 4 km to Frankfurt airport, using the 13-stage cascade impactor Nano-MOUDI (MSP Model-115). The chemical characterization of the ultrafine particles in the size range of 0.010-0.018 μm, 0.018-0.032 μm and 0.032-0.056 μm was accomplished by the development of an optimized filter extraction method. An UHPLC method for chromatographic separation of homologous series of hydrophobic and high molecular weight organic compounds, followed by heated electrospray ionization (ESI) and mass analysis using an Orbitrap high-resolution mass spectrometer was developed. Using a non-target screening, ~200 compounds were detected in the positive ionization mode after filtering, in order to ensure high quality of the obtained data. We determined the molecular formula of positively charged adducts ([M+H]<sup>+</sup>; [M+Na]<sup>+</sup>), and for each impaction stage we present molecular fingerprints (Molecular weight vs Retention time, Kroll-diagram, Van-Krevelen-diagram, Kendrick mass defect plot) in order to visualize the complex chemical composition. The negative ionization mode led only to the detection of a few compounds (<20) for which reason the particle characterization focuses on the positive ionization mode. We found that the majority of detected compounds belong to homologous series of two different kinds of organic esters, which are base stocks of aircraft lubrication oils. In reference to five different jet engine lubrication oils of various manufacturers, we identified the corresponding lubricant base stocks and their additives in the ultrafine particles by the use of matching retention time, exact mass and MS/MS fragmentation pattern of single organic molecules. As the relevance of the chemical composition of UFP regarding human health is depending on the mass contribution of each compound we strived for quantification of the jet engine oil compounds. This was achieved by standard addition of purchased original standards to the native sample extracts. Two amines serving as stabilizers, one organophosphate used as an anti-wear agent/metal deactivator and two ester base stocks were quantified. Quantification of the two homologous ester series was carried out using one ester compound and cross-calibration. The quantitative determination is burdened by the uncertainty regarding sampling artefacts in the Nano-MOUDI. Therefore we characterized the cascade impactor in a lab experiment using the ester standard. Particle size distribution measurements conducted parallel to the filter sampling enables the determination of jet engine oil contribution to the UFP mass. Results indicate that aircraft emissions strongly influence the mass balance of 0.010-0.018 μm particles. This contribution decreases for bigger sized particles (0.018-0.056 μm) as presumably more sources get involved. The hereby-introduced method allows the qualitative and quantitative assignment of aircraft emissions towards the chemical composition and total mass of airport related ultrafine particles.</p>

Identification and Source Attribution of Organic Compounds in Ultrafine Particles near Frankfurt International Airport

Analysing the composition of ambient ultrafine particles (UFP) is a challenging task due to the low mass and chemical complexity of small particles, yet it is a prerequisite for the identification of particle sources and the assessment of potential health risks. Here, we show the molecular characterization of UFP, based on cascade impactor (Nano-MOUDI) samples that were collected at an air quality monitoring station nearby one of Europe's largest airports in Frankfurt, Germany. At this station, particle-size-distribution measurements show enhanced number concentration of particles smaller than 50 nm during airport operating hours. We sampled the lower UFP fraction (0.010–0.018 μm; 0.018–0.032 μm; 0.032–0.056 μm) when the air masses arrived from the airport. We developed an optimized filter extraction procedure, used ultra-high performance liquid chromatography (UHPLC) for compound separation, and a heated electrospray ionization (HESI) source with an Orbitrap high-resolution mass spectrometer (HRMS) as a detector for organic compounds. A non-target screening detected ~200 organic compounds in the UFP fraction with sample-to-blank ratios larger than five. We identified the largest signals as homologous series of pentaerythritol esters (PEE) and trimethylolpropane esters (TMPE), which are base stocks of aircraft lubrication oils. We unambiguously attribute the majority of detected compounds to jet engine lubrication oils by matching retention times, high-resolution/accurate mass (HR/AM) measurements, and comparing MS/MS fragmentation patterns between both ambient samples and commercially available jet oils. For each UFP stage, we created molecular fingerprints to visualize the complex chemical composition of the organic fraction and their average carbon oxidation state. These graphs underline the presence of the homologous series of PEE and TMPE, and the appearance of jet oil additives (e.g. tricresyl phosphate (TCP)). Targeted screening on TCP confirmed the absence of the harmful tri-ortho isomer, while we identified a thermal transformation product of TMPE-based lubrication oil (trimethylolpropane phosphate (TMP-P)). Even though a quantitative determination of the identified compounds is limited, the presented method enables the qualitative detection of molecular markers for jet engine lubricants in UFP and thus strongly improves the source apportionment of UFP near airports.

Lubrication Oil Condition Monitoring and Remaining Useful Life Prediction with Particle Filtering

In order to reduce the costs of wind energy, it is necessary to improve the wind turbine availability and reduce the operational and maintenance costs. The reliability and availability of a functioning wind turbine depend largely on the protective properties of the lubrication oil for its drive train subassemblies such as the gearbox and means for lubrication oil condition monitoring and degradation detection. The wind industry currently uses lubrication oil analysis for detecting gearbox and bearing wear but cannot detect the functional failures of the lubrication oils. The main purpose of lubrication oil condition monitoring and degradation detection is to determine whether the oils have deteriorated to such a degree that they no longer fulfill their functions. This paper describes a research on developing online lubrication oil condition monitoring and remaining useful life prediction using particle filtering technique and commercially available online sensors. It first introduces the lubrication oil condition monitoring and degradation detection for wind turbines. Viscosity and dielectric constant are selected as the performance parameters to model the degradation of lubricants. In particular, the lubricant performance evaluation and remaining useful life prediction of degraded lubrication oil with viscosity and dielectric constant data using particle filtering are presented. A simulation study based on lab verified models is provided to demonstrate the effectiveness of the developed technique.

Problems of Selection of Lubricants for Ethylene High-Pressure Compressors. 4. Investigation of antifriction properties of naphtene and polyglycol oils during high loading of solid lubricant pair

The antifriction properties of naphtene and polyglycol oils during little loading with lubrication of pair bronze-tungsten-carbide-alloy WK-6 (WK-ll) and graphelon-20-WK-6 (WK-11) and high loading with lubrication of pair ball-bearing-high-chromium steel ShKh-15 - steel ShKh-15 are investigated. New correlations of viscous-and-thermal and antifriction properties of different polyglycol oils permit to creating effective composition on its base. The dependence of seizure loading during testing on FBFM on the molecular mass of different polyglycols, wear spot on the axial loading and boundary loading on concentration of additives in naphtene and mineral oils are found. The mean-square relative deviation of diameter of spot of wear from the spot by Hertz give generalization assessment of antiwear properties of lubrication oils.

Elemental analysis of jet engine lubrication oil and jet fuel using in-air PIXE

To understand the elemental characteristics of the exhaust particles from a jet aircraft, we performed an element analysis using an in-air PIXE system of the different lubrication oils of a jet engine (Mobil Jet Oil II, Mobil Jet Oil 254 and Eastman Turbo Oil 2380) and the jet fuel (JET A-1) to determine the effects on the exhaust particles. A high concentration (1,400–2,500 wt.-ppm) of P was detected from the analyzed three oil samples. The high concentration of P is probably due to the tricresyl phosphate (TCP: C[Formula: see text]H[Formula: see text]O4P) contained in the oil samples. The S concentrations of the JET A-1 fuel samples with different collection dates were in the range of [Formula: see text]10 to 530 wt.-ppm. These results aid in determining the component features of nanoparticles emitted from an aircraft.

Rheological behaviour of lubrication oils used in two-stroke marine engines

Purpose The purpose of this study is to investigate the rheological behaviour of commercial lubrication oils used for cylinder lubrication in two-stroke marine diesel engines. Furthermore, it is of interest to investigate whether the viscosity of lubrication oils is affected by different levels of alkalinity. Design/methodology/approach Viscosity measurements are performed using both rotational and capillary rheometry. It was possible to measure oil viscosity in the shear rate from 0.1 to 3,000 s−1 using rotational rheometry, whereas capillary rheometry allowed measurements in higher shear rates from 5 × 105 to 1.3 × 106 s−1 at 50°C. Findings The viscosity measurements show that the studied lubrication oils behave as a Newtonian fluid and that the viscosities are insensitive to the level of alkalinity. Furthermore, the viscosity/temperature dependency for the lubrication oils was found to fit the Arrhenius model. Originality/value This study presents useful information about the rheological behaviour of lubrication oils, more precisely how the oil properties are affected by shear rate, temperature and level of alkalinity. The value of this research is considered to be important for designing two-stroke diesel engines and cylinder lubrication systems.