Improved Polycyclic Aromatic Hydrocarbon and n-Alkane Determination in Speleothems through Cleanroom Sample Processing.

Interest in paleoenvironmental reconstructions from biomarkers in speleothems is increasing, thanks in part to the capacity of speleothems to grow continuously and to resist postdepositional alteration. In particular, the possibility exists to link high-resolution and accurately dated fire and vegetation records with isotopic data of climatic and paleoenvironmental interactions at the local and regional scale. However, the scarcity of existing methods for the quantification of organic molecules in stalagmites, together with the issues of sample availability, contamination, and low concentrations, complicate this approach. In this work, we developed a novel method for the simultaneous determination of 18 polycyclic aromatic hydrocarbons (PAHs) and 26 n-alkanes (C10-C35) and then tested it on "clean" calcite and aragonite stalagmite samples from cave KNI-51 in the Australian tropics. The method involves subsampling by using a hand-held drill, complete dissolution of the matrix in hydrochloric acid, then liquid-liquid extraction, and GC-MS analysis. Sample preparation was carried out in a 10 000 class clean room built entirely in stainless steel to avoid contamination. Detection limits were 0.3-9 ng for PAHs and 6-44 ng for n-alkanes. Measurable concentrations of fire-derived PAH compounds, namely, phenanthrene, pyrene, benzo( e)pyrene, and indeno(123- cd)pyrene, were detected in only one sample, which dates to the year ∼2004 CE, when a fire burned vegetation over the cave; n-alkanes were detected in all samples in the range C23-C35, with no odd-even preference.

Biomass burning source identification through molecular markers in cryoconites over the Tibetan Plateau.

Cryoconite is a dark, dusty aggregate of mineral particles, organic matter, and microorganisms transported by wind and deposited on glacier surfaces. It can accelerate glacier melting and alter glacier mass balances by reducing the surface albedo of glaciers. Biomass burning in the Tibetan Plateau, especially in the glacier cryoconites, is poorly understood. Retene, levoglucosan, mannosan and galactosan can be generated by the local fires or transported from the biomass burning regions over long distances. In the present study, we analyzed these four molecular markers in cryoconites of seven glaciers from the northern to southern Tibetan Plateau. The highest levels of levoglucosan and retene were found in cryoconites of the Yulong Snow Mountain and Tienshan glaciers with 171.4 ±â€¯159.4 ng g-1 and 47.0 ±â€¯10.5 ng g-1 dry weight (d.w.), respectively. The Muztag glacier in the central Tibetan Plateau contained the lowest levels of levoglucosan and retene with mean values of 59.8 ng g-1 and 0.4 ±â€¯0.1 ng g-1 d.w., respectively. In addition, the vegetation changes and the ratios of levoglucosan to mannosan and retene indicate that combustion of conifers significantly contributes to biomass burning of the cryoconites in the Yulong Snow Mountain and Tienshan glacier. Conversely, biomass burning tracers in cryoconites of Dongkemadi, Yuzhufeng, Muztag, Qiyi and Laohugou glaciers are derived from the combustion of different types of biomass including softwood, hardwood and grass.

GC-MS method for determining faecal sterols as biomarkers of human and pastoral animal presence in freshwater sediments.

In order to determine sterols and stanols in freshwater sediments to reconstruct the past presence of humans and pastoral animals, we developed an analytical method based on pressurised liquid extraction (PLE), clean-up performed using solid phase extraction (SPE) and sterol determination using gas chromatography-mass spectrometry (GC-MS) analysis. PLE extraction conditions were optimised using dichloromethane (DCM) and DCM/methanol mixtures. Clean-up was performed with 2 g silica SPE cartridges, and the concentrated extracts were eluted with 70 mL DCM. Extraction yield was evaluated using an in-house reference material spiked with (13)C-labelled cholesterol and aged for 10 days. In comparison with pre-extraction, where the sediment is extracted and then spiked with a known analyte concentration, this approach preserves the original composition of the sediment. DCM and DCM/methanol mixtures resulted in high extraction yields ranging from 86 to 92 % with good reproducibility (relative standard deviation (RSD) 5-8 %). PLE extraction yields obtained with DCM as the extracting solvent were about 1.5 times higher than extractions using an ultrasonic bath. The solvent extraction mixture and matrix composition strongly affected the solvent extraction composition where higher overall recoveries (70-80 %) for each compound were obtained with DCM. The extraction mixture and matrix composition also affected the analyte concentrations, resulting in a method precision ranging from 1 to 18 %. Diatomaceous earth spiked with 10 to 100 ng of sterols, and environmental samples fortified with suitable amounts of sterols provided apparent recovery values ranging from 90 to 110 %. We applied the method to environmental samples both close to and upstream from sewage discharge zones, resulting in substantially higher faecal sterol (FeSt) concentrations near the sewage. In addition, we also applied the method to a 37-cm freshwater sediment core in order to evaluate its applicability for obtaining vertical sterol profiles.

Gas-particle distributions, sources and health effects of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) in Venice aerosols.

Air samples were collected in Venice during summer 2009 and 2012 to measure gas and particulate concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs). PCB-11, considered a marker for non-Aroclor contamination of the environment, was found for the first time in the Venetian lagoon and in Europe. An investigation on sources has been conducted, evidencing traffic as the major source of PAHs, whereas PCBs have a similar composition to Aroclor 1248 and 1254; in 2009 a release of PCN-42 has been hypothesized. Toxicological evaluation by TCA and TEQ methods, conducted for the first time in Venice air samples, identified BaP, PCB-126 and PCB-169 as the most important contributors to the total carcinogenic activity of PAHs and the total dioxin-like activity of PCBs and PCNs.