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Increasing use of scrubbers on vessels for reduction of SOx emissions has led to environmental concerns due to discharge of partly persistent and toxic substances such as polycyclic aromatic compounds (PAC) into the sea. A comprehensive analysis of the dissolved and particulate phases of the discharge water from open and closed loop operations on four ships was performed. 71 PAC in the discharge waters varied in concentration and were associated with those of the fuels used, as they mainly originate in unburnt fuel. Closed loop discharge water showed higher PAC concentrations, especially of HMW PAC, which partly explains the larger toxic effects reported for this discharge. Alkylnaphthalenes and -phenanthrenes dominated in dissolved and particulate fractions, respectively. 14 NSO-PAC concentrations were relatively low. Alkylated derivatives of 4H-cyclopenta[4,5-def]phenanthrene and/or phenylnaphthalene were for the first time tentatively identified using GC-APLI-MS. The use of low-PAC fuels could significantly reduce PAC ship emissions.

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OBJECTIVE: Listeriosis is caused by the bacterium, Listeria monocytogenes, and is a significant health concern because of high hospitalization and mortality rates. This study reports seven cases of pregnancy-associated listeriosis diagnosed with matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry performed on infection-positive blood culture. METHODS: Blood culture-positive samples of seven patients whose pregnancy was complicated by Listeria infection and treated at Xuanwu Hospital of Capital Medical University between January 2016 and December 2021 were analyzed retrospectively. Strains identified by MALDI-TOF mass spectrometry were compared with colony identification results. Identification accuracy and consistency were assessed. RESULTS: A total of seven strains of Listeria were collected from seven pregnant women presented with fever (37.6-39.9°C). Clinical abnormalities included abnormal liver function, emaciation, hypoalbuminemia, hypocalcemia, hypokalemia, hyponatremia, ketosis, mild to moderate anemia, leukopenia, and thrombocytopenia. Compared with the traditional culture method, MALDI-TOF mass spectrometry led to much earlier identification (4-6 h vs. 3-4 days) with 100% identification accuracy. Of the seven pregnancies complicated by Listeria, only two led to live births. Of the five fetal deaths, three occurred in the second trimester. CONCLUSION: In this series of pregnancy-associated listeriosis cases, the fetal mortality rate was 71%. MALDI-TOF mass spectrometry is a valuable method that can identify Listeria from blood culture rapidly and accurately.

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The use of atmospheric pressure ionization (API) sources has become very popular for gas chromatography-mass spectrometry (GC-MS) determinations. GC-API-MS shows important advantages over traditional vacuum ionization sources such as a lower fragmentation preserving the molecular or quasi-molecular ion, the combination of GC separations with advanced mass spectrometers typically developed for liquid chromatography (LC) systems, a significantly higher sensitivity, or the reduction of costs due to the capability to use the same MS for both LC- and GC- couplings. For these reasons, the development of new API sources and GC-API-MS platforms has exponentially increased during the last years. Thus, this review is mainly focused on the last advances in GC-API-MS instrumentation. New setups and couplings on extensively reported API techniques as well as the development of new API sources for GC-MS coupling are thoroughly discussed. Moreover, novel ionization strategies have been reviewed to overcome some of the drawbacks of GC-API-MS methodologies.

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Detection of low-volatile explosives in concentrations below 10-14 g/cm3 is a great challenge for portable ion mobility spectrometers (IMS) and field asymmetric IMS (FAIMS). We study the capabilities of FAIMS detector with ultraviolet laser ionization combined with organic additives (dopants) toluene and 1-methylnaphtalene to sense nitro-explosives: trinitrotoluene (TNT) and low-volatile cyclonite (RDX) and nitropentaerythritol (PETN). Differential mobility coefficients were measured for target ion peaks of TNT, RDX and PETN. Presence of dopants in the sample results in multiple growth of ion yield at laser intensities lower than 2 × 107 W/cm2. Limits of detection with dopant-assisted laser ionization were determined: 4.7 × 10-16 g/cm3 for RDX and 9.8 × 10-15 g/cm3 for PETN. Obtained results propose a way to further improve sensitivity of detectors along with improvement of portability of current laser-based FAIMS prototypes by using less powerful and smaller lasers.

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Laser resonance ionization at the RISIKO 30 kV mass separator has been used to produce isotopically and isobarically pure and well quantified 222Rn emanation standards. Based upon laser-spectroscopic preparation studies, ion implantation into aluminum and tungsten targets has been carried out, providing overall implantation efficiencies of 40% up to 60%. The absolute implanted activity of 226Ra was determined by the technique of defined solid-angle α-particle spectrometry, where excellent energy resolution was observed. The 222Rn emanation coefficient of the produced targets was studied using α-particle and γ-ray spectrometry, and yielded results between 0.23 and 0.34, with relative uncertainty on the order of 1%. No dependence exceeding a 1% change of the emanation on humidity could be identified in the range of 15 %rH to 75 %rH, whereas there were hints of a slight correlation between the emanation and temperature. Additionally, and as expected, the emanation coefficient was found to be dependent on the target material as well as the implanted dose.

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Laser ionization mass spectrometry (LIMS) was one of the first practical methods developed for in situ analysis of the surfaces of solid samples. This review will encompass several aspects related to this analytical method. First, we will discuss the process of laser ionization, the influence of the laser type on its performance, and imaging capabilities of this method. In the second chapter, we will follow the historic development of LIMS instrumentation. After a brief overview of the first-generation instruments developed in 1960-1990 years, we will discuss in detail more recent designs, which appeared during the last 2-3 decades. In the last part of our review, we will cover the recent applications of LIMS for surface analysis. These applications include various types of analyses of solid inorganic, organic, and heterogeneous samples, often in combination with depth profiling and imaging capability.

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A single-particle mass spectrometer (SPMS) with laser ionization was constructed to determine the chemical composition of single particles in real time. The technique was evaluated using various polystyrene latex particles with different sizes (125 nm, 300 nm, 700 nm, and 1000 nm); NaCl, KCl, MgCO3, CaCO3, and Al2O3 particles with different chemical compositions; an internal mixture of NaCl and KCl; and an internal mixture of NaCl, KCl, and MgCl2 with different mixing states. The results show that the SPMS can be useful for the determination of chemical characteristics and mixing states of single particles in real time. The SPMS was then applied to obtain the chemical signatures of various combustion aerosols (diesel engine exhaust, biomass burning (rice straw), coal burning, and cooking (pork)) based on their single-particle mass spectra. Elemental carbon (EC)-rich and EC-organic carbon (OC) particles were the predominant particle types identified in diesel engine exhaust, while K-rich and EC-OC-K particles were observed among rice straw burning emissions. Only one particle type (ash-rich particles) was detected among coal burning emissions. EC-rich and EC-OC particles were observed among pork burning particles. The single-particle mass spectra of the EC or OC types of particles differed among various combustion sources. The observed chemical signatures could be useful for rapidly identifying sources of atmospheric fine particles. In addition, the detected chemical signatures of the fine particles may be used to estimate their toxicity and to better understand their effects on human health.

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Samarium-153 (153Sm) is a highly interesting radionuclide within the field of targeted radionuclide therapy because of its favorable decay characteristics. 153Sm has a half-life of 1.93 d and decays into a stable daughter nuclide (153Eu) whereupon ß- particles [E = 705 keV (30%), 635 keV (50%)] are emitted which are suitable for therapy. 153Sm also emits γ photons [103 keV (28%)] allowing for SPECT imaging, which is of value in theranostics. However, the full potential of 153Sm in nuclear medicine is currently not being exploited because of the radionuclide's limited specific activity due to its carrier added production route. In this work a new production method was developed to produce 153Sm with higher specific activity, allowing for its potential use in targeted radionuclide therapy. 153Sm was efficiently produced via neutron irradiation of a highly enriched 152Sm target (98.7% enriched, σth = 206 b) in the BR2 reactor at SCK CEN. Irradiated target materials were shipped to CERN-MEDICIS, where 153Sm was isolated from the 152Sm target via mass separation (MS) in combination with laser resonance enhanced ionization to drastically increase the specific activity. The specific activity obtained was 1.87 TBq/mg (≈ 265 times higher after the end of irradiation in BR2 + cooling). An overall mass separation efficiency of 4.5% was reached on average for all mass separations. Further radiochemical purification steps were developed at SCK CEN to recover the 153Sm from the MS target to yield a solution ready for radiolabeling. Each step of the radiochemical process was fully analyzed and characterized for further optimization resulting in a high efficiency (overall recovery: 84%). The obtained high specific activity (HSA) 153Sm was then used in radiolabeling experiments with different concentrations of 4-isothiocyanatobenzyl-1,4,7,10-tetraazacyclododecane tetraacetic acid (p-SCN-Bn-DOTA). Even at low concentrations of p-SCN-Bn-DOTA, radiolabeling of 0.5 MBq of HSA 153Sm was found to be efficient. In this proof-of-concept study, we demonstrated the potential to combine neutron irradiation with mass separation to supply high specific activity 153Sm. Using this process, 153SmCl3 suitable for radiolabeling, was produced with a very high specific activity allowing application of 153Sm in targeted radionuclide therapy. Further studies to incorporate 153Sm in radiopharmaceuticals for targeted radionuclide therapy are ongoing.

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Plutonium is a major contributor to the radiotoxicity in a long-term nuclear waste repository; therefore, many studies have focused on interactions of plutonium with the technical, geotechnical, and geological barriers of a possible nuclear waste storage site. In order to gain new insights into the sorption on surfaces and diffusion of actinides through these complex heterogeneous materials, a highly sensitive method with spatial resolution is required. Resonant laser secondary neutral mass spectrometry (Laser-SNMS) uses the spatial resolution available in time-of-flight secondary ion mass spectrometry (TOF-SIMS) in combination with the high selectivity, sensitivity, and low background noise of resonance ionization mass spectrometry (RIMS) and is, therefore, a promising method for the study and analysis of the geochemical behavior of plutonium in long-term nuclear waste storage. The authors present an approach with a combined setup consisting of a commercial TOF-SIMS instrument and a Ti:sapphire (Ti:Sa) laser system, as well as its optimization, characterization, and improvements compared to the original proof of concept by Erdmann et al. (2009). As a first application, the spatial distributions of plutonium and other elements on the surface of a pyrite particle and a cement thin section were measured by Laser-SNMS and TOF-SIMS, respectively. These results exemplify the potential of these techniques for the surface analysis of heterogeneous materials in the context of nuclear safety research.

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Acoustically levitated droplets have been suggested as compartmentalized, yet wall-less microreactors for high-throughput reaction optimization purposes. The absence of walls is envisioned to simplify up-scaling of the optimized reaction conditions found in the microliter volumes. A consequent pursuance of high-throughput chemistry calls for a fast, robust and sensitive analysis suited for online interrogation. For reaction optimization, targeted analysis with relatively low sensitivity suffices, while a fast, robust and automated sampling is paramount. To follow this approach, in this contribution, a direct coupling of levitated droplets to a homebuilt ion mobility spectrometer (IMS) is presented. The sampling, transfer to the gas phase, as well as the ionization are all performed by a single exposure of the sampling volume to the resonant output of a mid-IR laser. Once formed, the nascent spatially and temporally evolving analyte ion cloud needs to be guided out of the acoustically confined trap into the inlet of the ion mobility spectrometer. Since the IMS is operated at ambient pressure, no fluid dynamic along a pressure gradient can be employed. Instead, the transfer is achieved by the electrostatic potential gradient inside a dual ring electrode ion optics, guiding the analyte ion cloud into the first stage of the IMS linear drift tube accelerator. The design of the appropriate atmospheric pressure ion optics is based on the original vacuum ion optics design of Wiley and McLaren. The obtained experimental results nicely coincide with ion trajectory calculations based on a collisional model. Graphical Abstract.

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Polycyclic aromatic hydrocarbons (PAH) are a group of ubiquitous environmental pollutants among which some compounds show carcinogenic properties. The emission of PAH from anthropogenic and natural sources to the aquatic environment demands monitoring. In this study, ten different surface water samples were collected and analyzed for 48 different PAH compounds by gas chromatography-atmospheric-pressure-laser-ionization coupled to mass spectrometry (GC-APLI-MS) after liquid-liquid extraction. Results varied from 9.22 ng/L for fluoranthene in harbor water to 0.01 ng/L for 4-methylchrysene in Rhine river water. Overall low PAH concentrations were found in the samples. Toxic equivalent (TEQ) calculations were used to assess the potential environmental impact of the analyzed compounds. The results showed higher concentrations and TEQ for the samples from harbors in comparison to riverine and estuarine sampling locations. Suspected target analysis indicated the occurrence of alkylated PAH in the surface water samples.

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Polycyclic aromatic hydrocarbons containing at least 24 carbon atoms (≥C24-PAH) are often associated with pyrogenic processes such as combustion of fuel, wood or coal, and occur in the environment in diesel particulate matter, black carbon and coal tar. Some of the ≥C24-PAH, particularly the group of dibenzopyrenes (five isomers, six aromatic rings) are known to show high mutagenic and carcinogenic activita. Gas chromatography - mass spectrometry is a well-established method for the analysis of lower molecular weight PAH but is not optimally suited for the analysis of ≥C24-PAH due to their low vapor pressures. Also, hundreds of ≥C24-PAH isomers are possible but only a few compounds are commercially available as reference standards. Therefore, in this study, a combination of multidimensional liquid chromatography, UV-Vis diode array detection, PAH selective and highly sensitive atmospheric pressure laser ionization - mass spectrometry is used to detect and unequivocally identify PAH. For identification of PAH in two bituminous coals and one petrol coke sample, unique and compound specific UV-Vis spectra were acquired. It was possible to identify ten compounds (naphtho[1,2,3,4-ghi]perylene, dibenzo[b,ghi]perylene, dibenzo[e,ghi]perylene, dibenzo[cd,lm]perylene, benzo[a]coronene, phenanthrol[5,4,3,2-abcde]perylene, benzo[ghi]naphtho[8,1,2-bcd]perylene, benzo[pqr]naphtho[8,1,2-bcd]perylene, naphtho[8,1,2-abc]coronene and tribenzo[e,ghi,k]perylene) by comparison of acquired spectra with spectra from literature. Additionally, it was possible to detect similar distribution patterns in different samples and signals related to alkylated naphthopyrenes, naphthofluoranthenes or dibenzopyrenes. Subsequent effect-directed analysis of a bituminous coal sample using the microEROD (ethoxyresorufin-O-deethylase) bioassay showed high suitability and revealed lower EROD induction for the ≥C24-PAH (TEQ range 0.67-10.07 ng/g) than for the allover < C24-PAH containing fraction (TEQ 84.00 ng/g). Nevertheless, the toxicity of ≥C24-PAH has a significant impact compared with

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Nerve agent metabolites (NAMs) derived from alkyl methyl phosphonic acids, such as ethyl methylphosphonic acid (EMPA), isopropyl methylphosphonic acid (IMPA), and pinacolyl methylphosphonic acid (PMPA), were extracted from human urine using diethyl ether as an extractant. After exchanging the diethyl ether solvent to acetonitrile, the analytes were derivatized with 2-(bromomethyl)naphthalene (BMN). The reaction products of the BMN and NAMs, i.e., MN-EMPA, MN-IMPA, and MN-PMPA, were separated by gas chromatography (GC) and measured by mass spectrometry (MS) using a femtosecond laser emitting at 267 nm as the ionization source for resonance-enhanced two-photon ionization (RE2PI). The limits of detection (LOD) were <1 ng/mL for these analytes. The use of BMN increased the volatility of the analytes for separation by GC and also increased the ionization efficiency via the RE2PI process as the result of presence of a naphthalene functional group. A two-dimensional GC-MS display can be used for comprehensive analysis of NAMs, by-products, and impurities in the sample. Then, this approach could be used to confirm the use of chemical weapons and for forensic identification.

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The determination of the spatially resolved ion signal with atmospheric pressure laser ionization (APLI), which was introduced as distribution of ion acceptance (DIA), serves as a valuable tool for the understanding of complex and highly dynamical conditions in modern atmospheric pressure (AP) ion sources. DIA provides information about fluid dynamics, ion transport, and ion transformation processes in such sources and is an ideal basis for the validation of numerical models of the dynamics in the ion source enclosure.We present a fully automated setup for DIA measurements, which enabled us to acquire a comprehensive dataset of over 700 individual DIA measurements in a commercial AP ion source (Bruker Multi Purpose Ion Source, MPIS). Ion source parameters as voltages, gas heater temperatures and gas flows, were varied, and the effect of those parameters on the DIA of a chemically inert analyte, pyrene, was systematically investigated. It is shown that the response of the DIA is nonlinear and that gas dynamics largely dominates the ion transport in the ion source. Particularly, the position of the heated nebulizer, which is used to introduce one of two gas flows and the analyte into the ion source chamber, had a profound effect on the DIA. This suggests that the gas dynamics in the source switches between different states. The now available comprehensive DIA dataset reveals such critical effects and will guide further numerical modeling efforts to understand the details of the dynamics of ions in the source chamber. Graphical Abstract.

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The development of sensitive and specific analytical methods is critical for the discovery of molecular biomarkers, which assists disease diagnosis and understanding biological processes. Herein, a highly sensitive method is developed using antibody-conjugated plasmonic metal nanoparticles for the detection of targeted biomarkers down to low attomole level via coupling of immunoassay techniques with laser ionization mass spectrometry (LI-MS). The conjugated antibodies target specific antigens, while the metal nanoparticles act as mass tags and ion reservoirs for the signal amplification. With the characteristic localized surface plasmon resonance (LSPR) properties, gold (AuNPs) and silver nanoparticles (AgNPs) undergo explosive ionization upon laser irradiation to generate abundant characteristic mass reporter ions for strong MS signal amplification. With the antibody-conjugated NPs, detection of trace proteins in various biological samples with complex matrix environment, including urine, cell lysates, and animal tissues was demonstrated.

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Proceedings in environmental analytical chemistry of polycyclic aromatic hydrocarbons (PAH) in the past decades cover improvements in laboratory methods as well as new insights in the toxicology of single PAH compounds. A re-evaluation of the established list of 16 priority PAH published by the U. S. Environmental Protection Agency seems overdue. In this study we have applied PAH analysis by atmospheric pressure laser ionization - mass spectrometry (APLI-MS) to NIST 1941b, NIST 1649b, BAM CC013a and IRMM BCR 535 giving further references in addition to the certificates of analysis. Gas chromatography enables to distinguish between different alkylated PAH derivatives whereas liquid chromatography additionally allows detection of PAH tentatively with six or more aromatic rings on the level of chemical formula. For an optimal isomer-specific differentiation, LC-APLI-MS should be used in combination with fluorescence detection. Distribution patterns of 6 and 7-ring PAH are presented for urban dust, marine and harbor sediments and the soil sample. Additionally, a set of 14 nitrogen, sulfur and oxygen-containing polycyclic aromatic compounds were analyzed by APLI and quantified in all reference materials for the first time.

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For the first time gas chromatography (GC) coupled to atmospheric pressure laser ionization-mass spectrometry (APLI-MS) has been applied to the analysis of trans-anti-benzo[a]pyrene-tetraol (BaP-tetraol) formed from anti-benzo[a]pyrene diolepoxide (BPDE), the ultimate carcinogen of benzo[a]pyrene. This tetraol is considered to be an ideal urinary biomarker for polycyclic aromatic hydrocarbon (PAH) exposure as it reflects internal body burden and potentially adverse health effects. Optimization of the derivatization and the instrumental set-up led to an instrumental LOD of 0.5 fg, an improvement of the lowest instrumental LOD reported in literature of 6.4 fg by a factor of 10. The optimized procedure includes derivatization of hydroxyl groups using methyl iodide and cool on-column injection to prevent degradation of the analyte. First measurements of urine samples demonstrate that the method is capable of detecting BaP-tetraol in human urine collected from both smokers and non-smokers. Although results of analysis indicate a certain underestimation compared with literature data, this method can be expected to serve as an excellent method for the analysis of the biomarker BaP-tetraol in the future if an adequate internal standard such as 13C-labeled BaP-tetraol is applied.

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Using lasers in ion mobility spectrometry offers a lot of advantages compared to standard ionization sources. Especially, the ion yield can be drastically increased. It can, however, reach levels where the Coulomb repulsion leads to unwanted side effects. Here, we investigate how the Coulomb repulsion can be detected apart from the typical signal broadening by measuring effects created already in the reaction region and comparing them with corresponding finite element method simulations.

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The main advantages of laser sampling are associated with following features: sample preparations as well as consumables are not needed, low risk of sample contamination, good spatial resolution. In mass spectrometry, high laser irradiance can be used for both ablation and ionization processes. The method is especially profitable in time-of-flight mass spectrometry. A new principle of constructing laser ionization time-of-flight mass spectrometer based on wedge-shaped ion mirrors and the absence of electrostatic ion acceleration before mass analysis is discussed. Among advantages of the analyzer there are ability to provide temporal focusing of ions in a wide energy range (±20%), compactness of the analyzer, and minimization of the requirements for power supplies. The approach is expected to be profitable for standardless elemental analysis of solid samples, which should be possible at laser irradiation power density more than 3 × 109 W/cm2 that ensures complete ionization of all elements in a laser plasma. The analytical signal of each element is formed as the sum of the signals for all charge states and the energy scan of the mass spectra is provided.

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We present a proof-of-principle approach for discriminating chiral enantiomers based on the phenomenon of multiphoton photoelectron circular dichroism. A novel stereo detection setup was used to measure the number of photoelectrons emitted from chiral molecules in directions parallel or anti-parallel to the propagation of the ionising femtosecond laser pulses. In this study, we show how these asymmetries in the ketones camphor and fenchone depend upon the ellipticity of the laser pulses and the enantiomeric excess of the sample. By using a high repetition rate femtosecond laser, enantiomer excesses with uncertainties at the few-percent level could be measured in close to real-time. As the instrument is compact, and commercial turnkey femtosecond lasers are readily available, the development of a stand-alone chiral analysis instrument for a range of applications is now possible.