Direct Injection Liquid Chromatography High-Resolution Mass Spectrometry for Determination of Primary and Secondary Terrestrial and Marine Biomarkers in Ice Cores

Many atmospheric organic compounds are long-lived enough to be transported from their sources to polar regions and high mountain environments where they can be trapped in ice archives. While inorganic components in ice archives have been studied extensively to identify past climate changes, organic compounds have rarely been used to assess paleo-environmental changes, mainly due to the lack of suitable analytical methods. This study presents a new method of direct injection HPLC-MS analysis, without the need of pre-concentrating the melted ice, for the determination of a series of novel biomarkers in ice-core samples indicative of primary and secondary terrestrial and marine organic aerosol sources. Eliminating a preconcentration step reduces contamination potential and decreases the required sample volume thus allowing a higher time resolution in the archives. The method is characterised by limits of detections (LODs) in the range of 0.01-15 ppb, depending on the analyte, and accuracy evaluated through an interlaboratory comparison. We find that many components in secondary organic aerosols (SOA) are clearly detectable at concentrations comparable to those previously observed in replicate preconcentrated ice samples from the Belukha glacier, Russian Altai Mountains. Some compounds with low recoveries in preconcentration steps are now detectable in samples with this new direct injection method significantly increasing the range of environmental processes and sources that become accessible for paleo-climate studies

Direct target and non-target analysis of urban aerosol sample extracts using atmospheric pressure photoionisation high-resolution mass spectrometry

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous atmospheric pollutants of high concern for public health. In the atmosphere they undergo oxidation, mainly through reactions with center dot OH and NOx to produce nitro- and oxygenated (oxy-) derivatives. In this study, we developed a new method for the detection of particle-bound PAHs, nitro-PAHs and oxy-PAHs using direct infusion into an atmospheric pressure photoionisation high-resolution mass spectrometer (APPI-HRMS). Method optimisation was done by testing different source temperatures, gas flow rates, mobile phases and dopants. Samples were extracted with methanol, concentrated by evaporation and directly infused in the APPI source after adding toluene as dopant. Acquisition was performed in both polarity modes. The method was applied to target analysis of seasonal PM2.5 samples from an urban background site in Padua (Italy), in the Po Valley, in which a series of PAHs, nitro- and oxy-PAHs were detected. APPI-HRMS was then used for non-target analysis of seasonal PM2.5 samples and results compared with nano-electrospray ionisation (nanoESI) HRMS. The results showed that, when samples were characterised by highly oxidised organic compounds, including S-containing compounds, like in summer samples, APPI did not bring any additional information with respect to nanoESI in negative polarity (nanoESI(-)). Conversely, for winter samples, APPI(-) could detect a series of aromatic and poly-aromatic compounds, mainly oxidised and nitrogenated aromatics, that were not otherwise detected with nanoESI. (C) 2019 Elsevier Ltd. All rights reserved

DNA barcoding of Ceramiales (Rhodophyta) around the Maltese islands reveals hidden biodiversity in the central Mediterranean

The genetic biodiversity of Mediterranean macroalgae is generally understudied, a fact which is especially important in the case of morphologically cryptic taxa. As a result, it is often challenging to compare DNA barcodes from Mediterranean samples to references in online databases since, very often, no close hits are available. At a regional scale, of around 1124 records of algae in the Mediterranean Sea, only 114 species have been barcoded.peer-reviewe

Synthesis and biological studies on dinuclear gold(I) complexes with Di-(N-Heterocyclic Carbene) ligands functionalized with carbohydrates

The design of novel metal complexes with N-heterocyclic carbene (NHC) ligands that display biological activity is an active research field in organometallic chemistry. One of the possible approaches consists of the use of NHC ligands functionalized with a carbohydrate moiety. Two novel Au(I)-Au(I) dinuclear complexes were synthesized; they present a neutral structure with one bridging diNHC ligand, having one or both heterocyclic rings decorated with a carbohydrate functionality. With the symmetric diNHC ligand, the dicationic dinuclear complex bearing two bridging diNHC ligands was also synthesized. The study was completed by analyzing the antiproliferative properties of these complexes, which were compared to the activity displayed by similar mononuclear Au(I) complexes and by the analogous bimetallic Au(I)-Au(I) complex not functionalized with carbohydrates

Novel correlations between spectroscopic and morphological properties of activated carbons from waste coffee grounds

Massive quantities of spent coffee grounds (SCGs) are generated by users around the world. Different processes have been proposed for SCG valorization, including pyrolytic processes to achieve carbonaceous materials. Here, we report the preparation of activated carbons through pyrolytic processes carried out under different experimental conditions and in the presence of various porosity activators. Textural and chemical characterization of the obtained carbons have been achieved through Brunauer–Emmett–Teller (BET), ESEM,13C solid state NMR, XPS, XRD, thermogravimetric and spectroscopic determinations. The aim of the paper is to relate these data to the preparation method, evaluating the correlation between the spectroscopic data and the physical and textural properties, also in comparison with the corresponding data obtained for three commercial activated carbons used in industrial adsorption processes. Some correlations have been observed between the Raman and XPS data

Mass spectrometry-based “omics” technologies for the study of gestational diabetes and the discovery of new biomarkers

Gestational diabetes (GDM) is one of the most common complications occurring during pregnancy. Diagnosis is performed by oral glucose tolerance test, but harmonized testing methods and thresholds are still lacking worldwide. Short-term and long-term effects include obesity, type 2 diabetes, and increased risk of cardiovascular disease. The identification and validation of sensitidve, selective, and robust biomarkers for early diagnosis during the first trimester of pregnancy are required, as well as for the prediction of possible adverse outcomes after birth. Mass spectrometry (MS)-based omics technologies are nowadays the method of choice to characterize various pathologies at a molecular level. Proteomics and metabolomics of GDM were widely investigated in the last 10 years, and various proteins and metabolites were proposed as possible biomarkers. Metallomics of GDM was also reported, but studies are limited in number. The present review focuses on the description of the different analytical methods and MS-based instrumental platforms applied to GDM-related omics studies. Preparation procedures for various biological specimens are described and results are briefly summarized. Generally, only preliminary findings are reported by current studies and further efforts are required to determine definitive GDM biomarkers

Quality issues in Water Sampling, Sample Pre-treatment and Monitoring

One of the first books to cover transformation products, rather than primary compounds, Transformation Products of Emerging Contaminants in the Environment gathers, specifies, synthesizes, and advances existing knowledge of the most important transformation product (TPs) of the main groups of emerging contaminants with potential concern to human health and the environment. This two-volume set for researchers and professionals covers the sources of TPs of emerging contaminants and their environmental behavior, their occurrence and effects on urban and marine environments, risk assessment and management, and technologies and strategies available for control

Single-Walled Carbon Nanohorns as Boosting Surface for the Analysis of Low-Molecular-Weight Compounds by SALDI-MS

Limits of Matrix-Assisted Laser Desorption Ionization (MALDI) mass spectrometry (MS) in the study of small molecules are due to matrix-related interfering species in the low m/z range. Single-walled carbon nanohorns (SWCNH) were here evaluated as a specific surface for the rapid analysis of amino acids and lipids by Surface-Assisted Laser Desorption Ionization (SALDI). The method was optimized for detecting twenty amino acids, mainly present as cationized species, with the [M+K]+ response generally 2-time larger than the [M+Na]+ one. The [M+Na]+/[M+K]+ signals ratio was tentatively correlated with the molecular weight, dipole moment and binding affinity, to describe the amino acids’ coordination ability. The SWCNH-based surface was also tested for analyzing triglycerides in olive oil samples, showing promising results in determining the percentage composition of fatty acids without any sample treatment. Results indicated that SWCNH is a promising substrate for the SALDI-MS analysis of low molecular weight compounds with different polarities, enlarging the analytical platforms for MALDI applications