Elena Argiriadis

Development of a method for simultaneous analysis of PCDDs, PCDFs, PCBs, PBDEs, PCNs and PAHs in Antarctic air

The development of a unique analytical method for the determination of five classes of persistent organic pollutants (POPs) in atmospheric gas and the particle phase through gas chromatography coupled to high-resolution mass spectrometry is presented. Every step of the pre-analytical and analytical optimization process is described. Great effort was put into simplifying the traditional techniques, with reference to EPA and literature methods. Automated instruments were used for sample extraction and cleanup in order to enhance repeatability and reduce contamination risks. Unlike most common approaches, no separation of the analytes was performed before the GC analysis in order to avoid sample fractionation and to save time and materials. This allowed low instrumental and method detection limits (pg to sub-pg) to be achieved. Accuracy and precision were tested by fortifying the matrix and analysing standard reference materials (NIST SRM 1649b Urban Dust and 2585 Organic Contaminants in House Dust). The method was applied to five samples from Terra Nova Bay, Antarctica. Concentrations of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), polybrominated diphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs) are presented. Lighter compounds dominate the distribution and are mainly present in the gaseous phase. The observed pattern may be attributable to long-range transport. Results are in general agreement with literature data, where available.

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.

Fire and human record at Lake Victoria, East Africa, during the Early Iron Age: Did humans or climate cause massive ecosystem changes?

Organic molecular markers determined in a sediment core (V95-1A-1P) from Lake Victoria (East Africa) were used to reconstruct the history of human impact and regional fire activity during the Early Iron Age (~2400 to ~1100 yr BP). Fire history was reconstructed using levoglucosan and polycyclic aromatic hydrocarbons (PAHs) as markers for biomass burning that demonstrate two distinct fire periods peaking at 1450–1700 and 1850–2050 cal. yr BP. A partial correlation between levoglucosan and PAHs is interpreted as different transport behaviors and burn temperatures affecting the proxies. A fecal sterol index (CoP-Index) indicates the presence of humans near the lakeshore, where the CoP-Index lags a few centuries behind the fire peaks. The CoP-Index peaks between 1850 and1950 cal. yr BP and between 1400 and 1500 cal. yr BP. Retene, a PAH that indicates softwood combustion, differs from other PAHs and levoglucosan by abruptly increasing at ~1650 cal. yr BP and remaining high until 1200 cal. yr BP. This increase may potentially signal human activity in that the development of metallurgy and/or ceramic production requires highly efficient fuels. However, this increase in retene occurs at the same time as severe drought events centered at ~1500 and ~2000 yr BP where the droughts and associated woodland to grassland transition may have resulted in more intense fires. The grassland expansion could have created favorable conditions for human activities and triggered settlement growth that in turn may have created a positive feedback for further landscape opening.

Characterization of metals in air and soil near a steel making plant in the North part of Italy

Purpose – The purpose of this paper is to define suitable tracers that are particularly significant in assessing the impact on the surrounding environment caused by a steel making plant. Design/methodology/approach – The authors focussed on the detection and quantification of inorganic pollutants such as heavy metals in the soil and in the air in the surrounding area of the steel making plant. The presented data, concerning a plant in the North part of Italy, come from an approach that took into account the advantages of different devices and sampling criteria: apart from conventional devices, two kinds of deposimeters have been used (for characterizing either total or wet/dry depositions). Their locations have been chosen taking into account the distance from the plant. Findings – The paper demonstrates that the presence of diffused emissions plays an important (negative) role still today; thus a modern plant should reduce this kind of emission in order to be accepted from the population living in the su...

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 ± 159.4 ng g-1 and 47.0 ± 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 ± 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.

Lake sediment fecal and biomass burning biomarkers provide direct evidence for prehistoric human-lit fires in New Zealand

Deforestation associated with the initial settlement of New Zealand is a dramatic example of how humans can alter landscapes through fire. However, evidence linking early human presence and land-cover change is inferential in most continental sites. We employed a multi-proxy approach to reconstruct anthropogenic land use in New Zealand’s South Island over the last millennium using fecal and plant sterols as indicators of human activity and monosaccharide anhydrides, polycyclic aromatic hydrocarbons, charcoal and pollen as tracers of fire and vegetation change in lake-sediment cores. Our data provide a direct record of local human presence in Lake Kirkpatrick and Lake Diamond watersheds at the time of deforestation and a new and stronger case of human agency linked with forest clearance. The first detection of human presence matches charcoal and biomarker evidence for initial burning at c. AD 1350. Sterols decreased shortly after to values suggesting the sporadic presence of people and then rose to unprecedented levels after the European settlement. Our results confirm that initial human arrival in New Zealand was associated with brief and intense burning activities. Testing our approach in a context of well-established fire history provides a new tool for understanding cause-effect relationships in more complex continental reconstructions.