Sea ice fluctuations in the Baffin Bay and the Labrador Sea during glacial abrupt climate changes.

Sea ice decline in the North Atlantic and Nordic Seas has been proposed to contribute to the repeated abrupt atmospheric warmings recorded in Greenland ice cores during the last glacial period, known as Dansgaard-Oeschger (D-O) events. However, the understanding of how sea ice changes were coupled with abrupt climate changes during D-O events has remained incomplete due to a lack of suitable high-resolution sea ice proxy records from northwestern North Atlantic regions. Here, we present a subdecadal-scale bromine enrichment (Brenr) record from the NEEM ice core (Northwest Greenland) and sediment core biomarker records to reconstruct the variability of seasonal sea ice in the Baffin Bay and Labrador Sea over a suite of D-O events between 34 and 42 ka. Our results reveal repeated shifts between stable, multiyear sea ice (MYSI) conditions during cold stadials and unstable, seasonal sea ice conditions during warmer interstadials. The shift from stadial to interstadial sea ice conditions occurred rapidly and synchronously with the atmospheric warming over Greenland, while the amplitude of high-frequency sea ice fluctuations increased through interstadials. Our findings suggest that the rapid replacement of widespread MYSI with seasonal sea ice amplified the abrupt climate warming over the course of D-O events and highlight the role of feedbacks associated with late-interstadial seasonal sea ice expansion in driving the North Atlantic ocean-climate system back to stadial conditions.

Fast Liquid Chromatography Coupled with Tandem Mass Spectrometry for the Analysis of Vanillic and Syringic Acids in Ice Cores.

The development of new analytical systems and the improvement of the existing ones to obtain high-resolution measurements of chemical markers in samples from ice cores, is one of the main challenges the paleoclimatic scientific community is facing. Different chemical species can be used as markers for tracking emission sources or specific environmental processes. Although some markers, such as methane sulfonic acid (a proxy of marine productivity), are commonly used, there is a lack of data on other organic tracers in ice cores, making their continuous analysis analytically challenging. Here, we present an innovative combination of fast liquid chromatography coupled with tandem mass spectrometry (FLC-MS/MS) to continuously determine organic markers in ice cores. After specific optimization, this approach was applied to the quantification of vanillic and syringic acids, two specific markers for biomass burning. Using the validated method, detection limits of 3.6 and 4.6 pg mL-1 for vanillic and syringic acids, respectively, were achieved. Thanks to the coupling of FLC-MS/MS with the continuous flow analytical system, we obtained one measurement every 30 s, which corresponds to a sampling resolution of a sample every 1.5 cm with a melting rate of 3.0 cm min-1. To check the robustness of the method, we analyzed two parallel sticks of an alpine ice core over more than 5 h. Vanillic acid was found with concentrations in the range of picograms per milliliter, suggesting the combustion of coniferous trees, which are found throughout the Italian Alps.

Quantification and characterization of additives, plasticizers, and small microplastics (5-100 µm) in highway stormwater runoff.

Highway stormwater (HSW) runoff is a significant pathway for transferring microplastics from land-based sources to the other surrounding environmental compartments. Small microplastics (SMPs, 5-100 µm), additives, plasticizers, natural, and nonplastic synthetic fibers, together with other components of micro-litter (APFs), were assessed in HSW samples via Micro-FTIR; oleo-extraction and purification procedures previously developed were optimized to accomplish this goal. The distribution of SMPs and APFs observed in distinct HSW runoff varied significantly since rainfall events may play a crucial role in the concentration and distribution of these pollutants. The SMPs' abundance varied from 11932 ± 151 to 18966 ± 191 SMPs/L. The dominating polymers were vinyl ester (VE), polyamide 6 (PA6), fluorocarbon, and polyester (PES). The APFs' concentrations ranged from 12825 ± 157 to 96425 ± 430 APFs/L. Most APFs originated from vehicle and tire wear (e.g., Dioctyl adipate or 5-Methyl-1H-benzotriazole). Other sources of these pollutants might be pipes, highway signs, packaging from garbage debris, road marking paints, atmospheric deposition, and other inputs. Assessing SMPs in HSW runoff can help evaluating the potential threat they may represent to receiving water bodies and air compartments. Besides, APFs in HSW runoff may be efficient proxies of macro- and microplastic pollution.

Correction: Spatiotemporal distribution and speciation of silver nanoparticles in the healing wound.

Correction for 'Spatiotemporal distribution and speciation of silver nanoparticles in the healing wound' by Marco Roman et al., Analyst, 2020, 145, 6456-6469, DOI: 10.1039/D0AN00607F.

Fragrance materials (FMs) affect the larval development of the copepod Acartia tonsa: An emerging issue for marine ecosystems.

Fragrance materials (FMs) are used in a variety of detergents and cosmetics, including household and personal care products. Despite their widespread use and the growing evidence of their occurrence in surface waters worldwide, very little is known about their toxicity towards marine species, including a key component of the marine food webs such as copepods. Thus, we investigated the toxicity of six of the more long-lasting and stable commercial fragrances, including Amyl Salicylate (AMY), Oranger Crystals (ORA), Hexyl Salicylate (HEX), Ambrofix (AMB), Peonile (PEO), and Benzyl Salicylate (BZS), to assess their ability to impair the larval development of the calanoid copepod Acartia tonsa. FMs inhibited the development of A. tonsa significantly at concentrations by far lower than the effect-concentrations reported in the literature for aquatic species. The more toxic FMs were HEX (EC50 = 57 ng L-1), AMY (EC50 = 131 ng L-1) and ORA (EC50 = 766 ng L-1), while the other three compounds exerted toxic effects at concentrations higher than 1000 ng L-1 (LOEC at 1000 ng L-1 for PEO and BZS, and at 10,000 ng L-1 for AMB). Early life-stage mortality was unaffected by FMs at all the tested concentrations. A comparison with water concentrations of FMs reported in the literature confirmed that FMs, especially HEX and AMY, may act as contaminants of potential concern in many aquatic habitats, including urban areas and remote and polar environments.

Spatiotemporal distribution and speciation of silver nanoparticles in the healing wound.

The medical application of nanomaterials is growing fast. Amongst the most widely used, silver nanoparticles are antimicrobial agents whose key application is the care of burns and chronic wounds. Still, their absorption, distribution, metabolism and excretion behaviour in vivo has not yet been systematically investigated. We collected full-profile specimens of skin from four hospital patients with mid-to-deep thickness burns or equivalent skin wounds, treated with dressings containing silver nanoparticles or silver sulfadiazine. Synchrotron radiation µXRF/µXANES and laser ablation-ICP-MS were used to provide the first semi-quantitative/high resolution direct information on the spatiotemporal distribution and speciation of silver in vivo. The metal was rapidly released onto the wound surface, followed by a significant structure-dependent penetration into the damaged tissues. This was accompanied by sequential processes of metallic silver dissolution, chloride complexation, change to metal-thiol protein complexes, and final mobilization into deeper skin layers towards the vascular networks. Complete local clearance of silver was observed after 12 days of treatment in the case of full healing. The results provide a complete insight into the dynamics of silver in real human wounds, and a new basis for the design of innovative silver nanomaterials with optimal antibacterial efficacy and minimized risk for the patient.

A microbial ecosystem beneath the West Antarctic ice sheet.

Liquid water has been known to occur beneath the Antarctic ice sheet for more than 40 years, but only recently have these subglacial aqueous environments been recognized as microbial ecosystems that may influence biogeochemical transformations on a global scale. Here we present the first geomicrobiological description of water and surficial sediments obtained from direct sampling of a subglacial Antarctic lake. Subglacial Lake Whillans (SLW) lies beneath approximately 800 m of ice on the lower portion of the Whillans Ice Stream (WIS) in West Antarctica and is part of an extensive and evolving subglacial drainage network. The water column of SLW contained metabolically active microorganisms and was derived primarily from glacial ice melt with solute sources from lithogenic weathering and a minor seawater component. Heterotrophic and autotrophic production data together with small subunit ribosomal RNA gene sequencing and biogeochemical data indicate that SLW is a chemosynthetically driven ecosystem inhabited by a diverse assemblage of bacteria and archaea. Our results confirm that aquatic environments beneath the Antarctic ice sheet support viable microbial ecosystems, corroborating previous reports suggesting that they contain globally relevant pools of carbon and microbes that can mobilize elements from the lithosphere and influence Southern Ocean geochemical and biological systems.

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.

Simultaneous determination of halogenated contaminants and polycyclic aromatic hydrocarbons: a multi-analyte method applied to filter-feeding edible organisms.

This study develops and validates a novel analytical approach for the simultaneous determination of 127 polychlorinated biphenyls (PCBs), together with 6 polychlorinated naphthalenes (PCNs) and 16 polycyclic aromatic hydrocarbons (PAHs). PCBs, PCNs, and PAHs were subjected to a unique pretreatment protocol and were simultaneously determined in a single chromatographic run, using GC-MS, in environmental marine samples of mussels and clams. The results of the validation experiments, which were performed on the standard reference materials (NIST SRM 1974C - slurried matrix and NIST SRM 2977 - freeze-dried matrix), were in accordance with the certified and the reference values. The repeatability of the method for all target compounds, expressed as mean relative standard deviations, ranged from 2.5 to 5.1 % for PCBs, from 3.9 to 5.5 % for PCNs, and from 8.6 to 17.9 % for PAHs; the first value of each pair refers to the freeze-dried matrix and the second to the fresh one, for each of the classes of compounds examined. The quantification limits were in the range of 0.2-6 pg for PCBs, 0.4-8 pg for PCNs, and 0.2-15 pg for PAHs (on column). The method recoveries yielded good results (62 ± 19 % for the freeze-dried matrix and 60 ± 14 % for the fresh one) and were not significantly reduced by adopting a single analytical protocol compared with the use of different group-specific analytical methods. No serious interferences were encountered and good selectivity was achieved. These results show that this method allows one to increase the laboratory sample throughput while requiring a small amount of tissue and saving time. Graphical Abstract Simultaneous determination of halogenated contaminants and polycyclic aromatic hydrocarbons: a multianalyte method applied to filter-feeding edible organisms.

Direct immersion solid-phase microextraction with gas chromatography and mass spectrometry for the determination of specific biomarkers of human sweat in melted snow.

To provide a reliable tool for investigating diffusion processes of the specific components of the human odor 3-hydroxy-3-methylhexanoic acid and 3-methyl-3-sulfanylhexan-1-ol through the snowpack, we developed and optimized an analytical method based on direct immersion solid-phase microextraction followed by gas chromatography with mass spectrometry. Direct immersion solid-phase microextraction was performed using polyacrylate fibers placed in aqueous solutions containing 3-hydroxy-3-methylhexanoic acid and 3-methyl-3-sulfanylhexan-1-ol. After optimization, absorption times of 120 min provided a good balance to shorten the analysis time and to obtain suitable amounts of extractable analytes. The extraction efficiency was improved by increasing the ionic strength of the solution. Although the absolute extraction efficiency ranged between 10 and 12% for 3-hydroxy-3-methylhexanoic acid and 2-3% for 3-methyl-3-sulfanylhexan-1-ol, this method was suitable for analyzing 3-hydroxy-3-methylhexanoic acid and 3-methyl-3-sulfanylhexan-1-ol concentrations of at least 0.04 and 0.20 ng/mL, respectively. The precision of the direct immersion solid-phase microextraction method ranged between 8 and 16%. The variability within a batch of six fibers was 10-18%. The accuracy of the method provided values of 88-95 and 86-101% for 3-hydroxy-3-methylhexanoic acid and 3-methyl-3-sulfanylhexan-1-ol, respectively. The limit of detection (and quantification) was 0.01 ng/mL (0.04 ng/mL) for 3-hydroxy-3-methylhexanoic acid and 0.06 ng/mL (0.20 ng/mL) for 3-methyl-3-sulfanylhexan-1-ol. The signal versus concentration was linear for both compounds (r(2) = 0.973-0.979). The stability of these two compounds showed that 3-hydroxy-3-methylhexanoic acid was more stable in water than 3-methyl-3-sulfanylhexan-1-ol. We applied the method to environmental samples in correspondence with an olfactory target buried previously.

Fast and Sensitive Method for Determination of Domoic Acid in Mussel Tissue.

Domoic acid (DA), a neurotoxic amino acid produced by diatoms, is the main cause of amnesic shellfish poisoning (ASP). In this work, we propose a very simple and fast analytical method to determine DA in mussel tissue. The method consists of two consecutive extractions and requires no purification steps, due to a reduction of the extraction of the interfering species and the application of very sensitive and selective HILIC-MS/MS method. The procedural method was validated through the estimation of trueness, extract yield, precision, detection, and quantification limits of analytical method. The sample preparation was also evaluated through qualitative and quantitative evaluations of the matrix effect. These evaluations were conducted both on the DA-free matrix spiked with known DA concentration and on the reference certified material (RCM). We developed a very selective LC-MS/MS method with a very low value of method detection limit (9 ng g(-1)) without cleanup steps.

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.

Cross calibration between XRF and ICP-MS for high spatial resolution analysis of ombrotrophic peat cores for palaeoclimatic studies.

Ombrotrophic peatlands are remarkable repositories of high-quality climatic signals because their only source of nutrients is precipitation. Although several analytical techniques are available for analysing inorganic components in peat samples, they generally provide only low-resolution data sets. Here we present a new analytical approach for producing high-resolution data on main and trace elements from ombrotrophic peat cores. Analyses were carried out on a 7-m-long peat core collected from Danta di Cadore, North-Eastern Italy (46° 34' 16″ N, 12° 29' 58″ E). Ca, Ti, Cr, Fe, Cu, Zn, Ga, Sr, Y, Cd, Ba and Pb were detected at a resolution of 2.5 mm with a non-destructive X-ray fluorescence core scanner (XRF-CS). Calibration and quantification of the XRF-CS intensities was obtained using collision reaction cell inductively coupled plasma quadruple mass spectrometry (CRC-ICP-QMS). CRC-ICP-QMS measurements were carried out on discrete samples at a resolution of 1 cm, after dissolution of 150-mg aliquots with 9 ml HNO3 and 1 ml HF at 220 °C in a microwave system. We compare qualitative XRF-CS and quantitative CRC-ICP-MS data and, however the several sources of variability of the data, develop a robust statistical approach to determine the R (2) and the coefficient of a simple regression model together with confidence intervals. Perfect positive correlations were estimated for Cd, Cr, Pb, Sr, Ti and Zn; high positive correlations for Ba (0.8954), Y (0.7378), Fe (0.7349) and Cu (0.7028); while moderate positive correlations for Ga (0.5951) and Ca (0.5435). With our results, we demonstrate that XRF scanning techniques can be used, together with other well-established geochemical techniques (such as ICP-MS), to produce high-resolution (up to 2.5 mm) quantitative data from ombrotrophic peat bog cores.

D- and L-amino acids in Antarctic lakes: assessment of a very sensitive HPLC-MS method.

Amino acids represent a fraction of organic matter in marine and freshwater ecosystems, and a source of carbon, nitrogen and energy. L-Amino acids are the most common enantiomers in nature because these chiral forms are used during the biosynthesis of proteins and peptide. To the contrary, the occurrence of D-amino acids is usually linked to the presence of bacteria. We investigated the distribution of L- and D-amino acids in the lacustrine environment of Terra Nova Bay, Antarctica, in order to define their natural composition in this area and to individuate a possible relationship with primary production. A simultaneous chromatographic separation of 40 L- and D-amino acids was performed using a chiral stationary phase based on teicoplainin aglycone (CHIROBIOTIC TAG). The chromatographic separation was coupled to two different mass spectrometers--an LTQ-Orbitrap XL (Thermo Fisher Scientific) and an API 4000 (ABSciex)--in order to investigate their quantitative performance. High-performance liquid chromatography coupled with mass spectrometry methods were evaluated through the estimation of their linear ranges, repeatability, accuracy and detection and quantification limits. The high-resolution mass spectrometer LTQ-Orbitrap XL presented detection limits between 0.4 and 7 µg L (-1), while the triple quadrupole mass spectrometer API 4000 achieved the best detection limits reported in the literature for the quantification of amino acids (between 4 and 200 ng L (-1)). The most sensitive method, HPLC-API 4000, was applied to lake water samples.

From the highway to receiving water bodies: identification and simultaneous quantification of small microplastics (< 100 µm) in highway stormwater runoff.

Highway stormwater (HSW) runoff is among the environment's most important sources of microplastics. This study aimed to characterize via vibrational spectroscopy and quantify SMPs (small microplastics < 100 µm) in HSW runoff from a trafficked highway entering a facility equipped with a filtration system and in those flowing out to the receiving water body near agricultural activities. Samples of the inlet runoff (from the highway) and outlet runoff (the discharge into the environment) were collected in different periods to investigate potential seasonal and spatial differences. The sampling, methodology, and analysis were thoroughly carried out to quantify and simultaneously identify SMPs via Micro-FTIR to obtain a specific novel dataset to assess the environmental quality of highway pollution. A significant difference between inlet and outlet samples was reported; the highest abundance in inlet samples was 39813 ± 277 SMPs L.1 (SW10 IN; average length of 77 µm), while the highest one in outlet samples was 15173 ± 171 SMPs L-1 (SW10 OUT; SMPs' average length of 63 µm). Polyamide 6 (PA 6) and High-Density Polyethylene (HDPE) were predominant. Our results show that these HSW treatment plants, designed for managing regulated pollutants, can intercept SMPs, improving the quality of HSW runoff discharged into the environment.

Photodegradation of bisphenol A in water and ice: identification of products using three photosensitizers.

Bisphenol A (BPA) is a widespread organic micro-pollutant, found in most environments, including alpine and Arctic regions, and several matrices such as waters and aerosols. Polar regions are characterized by periods of intense irradiation with no sunset due to the continuous sunlight, while alpine areas, despite following the day-night cycle of mid-latitudes, also undergo strong irradiation. For such conditions, it is possible that a fraction of the BPA present in snow may degrade through direct photolysis, producing other unknown species with different environmental mobility and possible ecotoxic effects. Furthermore, the snowpack is rich in species (known as photosensitizers) that facilitate indirect photodegradation processes through reactions involving hydroxyl radicals  · OH , singlet oxygen (1O2), excited triplet states of the organic fraction (3CDOM*), and nitrite/nitrate. In this study, we investigated both direct and indirect photodegradation of BPA in the presence of specific photosensitizers producing  · OH , 1O2, 3CDOM*, and NO2- to specifically explore the products of the reaction. The study was conducted in both liquid water and ice, under light and dark conditions. Results, obtained by HPLC-HRMS, revealed that the matrix in which the reaction takes place, in addition to the photosensitizer used, may influence the degradation by-products. This allows for the possibility of distinguishing the reaction environment based on the identified product.

Characteristics and quantification of small microplastics (<100 µm) in seasonal svalbard snow on glaciers and lands.

Small microplastics (SMPs < 100 µm) can easily be transported over long distances far from their sources through the atmospheric pathways and reach even remote regions, including the Arctic. However, these sizes of MPs are mostly overlooked due to different analytical challenges; besides, their pathways through atmospheric depositions, such as snow depositions, are mostly unknown. The spatial variability in bulk snow samples was investigated for the first time in distinct sites (e.g., glaciers) near Ny Ålesund, the world-known northernmost permanent research settlement in the Svalbard Islands, to better comprehend the presence of SMP pollution in snow. Seasonal snow deposited over the tundra and the summits of different glaciers were also sampled. A sampling procedure was designed to obtain representative samples while minimizing plastic contamination, thanks to rigorous quality assurance and quality control protocol. SMPs' weight (µg SMP L-1) and deposition load (mg SMPs m-2) result from being lower in the remote glaciers, where they may be subject to long-range transport. The SMPs' minimum length was 20 µm, with the majority less than 100 µm. Regarding their size distribution, there was an increase in the size length deriving from the local input of the human presence near the scientific settlement. The presence of some polymers might be site-specific in relation to the pathways that affect their distribution at the sites studied. Also, from the snow surface layer collected at the same sites to evaluate the variability of SMPs during specific atmospheric deposition events, the results confirmed their higher weight and load in surface snow near the scientific settlement compared to the glaciers. The results will enhance the limited knowledge of the SMPs in polar atmospheric compartments and deposition processes.

Calibration of Arctic ice core bromine enrichment records for past sea ice reconstructions.

Bromine in ice cores has been proposed as a qualitative sea ice proxy to produce sea ice reconstructions for the polar regions. Here we report the first statistical validation of this proxy with satellite sea ice observations by combining bromine enrichment (with respect to seawater, Brenr) records from three Greenlandic ice cores (SIGMA-A, NU and RECAP) with satellite sea ice imagery, over three decades. We find that during the 1984-2016 satellite-era, ice core Brenr values are significantly correlated with first-year sea ice formed in the Baffin Bay and Labrador Sea supporting that the gas-phase bromine enrichment processes, preferentially occurring over the sea ice surface, are the main driver for the Brenr signal in ice cores. Moreover, in assessing Brenr's capability to record historical sea ice variability, we compare 20th-century Arctic Sea ice historical and proxy records with our reconstructions, based on an autoregressive-moving-average (ARMA) model, finding overall good agreement. While further enhancements are warranted, including site-specific calibrations and a comprehensive investigation into bromine transport-related concerns, this study presents a new method to quantitatively reconstruct past seasonal sea ice variability through bromine enrichment in ice cores.

Molecular markers of biomass burning in arctic aerosols.

Biomass burning is one of the most important sources of organic matter in the atmosphere as it affects the absorption and scattering of solar radiation, creates cloud condensation nuclei and possibly influences ice and snow albedo. Here we created and validated an analytical method using HPLC/(-)-ESI-MS/MS to determine phenolic compounds (PCLCs): vanillic acid, isovanillic acid, homovanillic acid, syringic acid, syringaldehyde, ferulic acid, p-coumaric acid, and coniferyl aldehyde at trace levels in particulate matter. We analyzed eighteen high-volume air samples from Ny Ålesund (Svalbard) collected during the boreal spring and summer of 2010. Biomass burning molecules including PCLCs (<0.49 µm, mean atmospheric concentration 6 pg m(-3)), levoglucosan (0.004 to 0.682 ng m(-3)) and acrylamide (32 fg m(-3) to 166 fg m(-3)) were present in the sampled aerosols. Levoglucosan concentrations, an unambiguous cellulose combustion tracer, derived from 2010 Russian fires. PCLCs levels in the Ny Alesund atmosphere in different size fractions reflected both long-range transport linked to biomass burning and a terrigenous local source.

Copper and tin isotopic analysis of ancient bronzes for archaeological investigation: development and validation of a suitable analytical methodology.

Although in many cases Pb isotopic analysis can be relied on for provenance determination of ancient bronzes, sometimes the use of "non-traditional" isotopic systems, such as those of Cu and Sn, is required. The work reported on in this paper aimed at revising the methodology for Cu and Sn isotope ratio measurements in archaeological bronzes via optimization of the analytical procedures in terms of sample pre-treatment, measurement protocol, precision, and analytical uncertainty. For Cu isotopic analysis, both Zn and Ni were investigated for their merit as internal standard (IS) relied on for mass bias correction. The use of Ni as IS seems to be the most robust approach as Ni is less prone to contamination, has a lower abundance in bronzes and an ionization potential similar to that of Cu, and provides slightly better reproducibility values when applied to NIST SRM 976 Cu isotopic reference material. The possibility of carrying out direct isotopic analysis without prior Cu isolation (with AG-MP-1 anion exchange resin) was investigated by analysis of CRM IARM 91D bronze reference material, synthetic solutions, and archaeological bronzes. Both procedures (Cu isolation/no Cu isolation) provide similar δ (65)Cu results with similar uncertainty budgets in all cases (±0.02-0.04 per mil in delta units, k = 2, n = 4). Direct isotopic analysis of Cu therefore seems feasible, without evidence of spectral interference or matrix-induced effect on the extent of mass bias. For Sn, a separation protocol relying on TRU-Spec anion exchange resin was optimized, providing a recovery close to 100 % without on-column fractionation. Cu was recovered quantitatively together with the bronze matrix with this isolation protocol. Isotopic analysis of this Cu fraction provides δ (65)Cu results similar to those obtained upon isolation using AG-MP-1 resin. This means that Cu and Sn isotopic analysis of bronze alloys can therefore be carried out after a single chromatographic separation using TRU-Spec resin. Tin isotopic analysis was performed relying on Sb as an internal standard used for mass bias correction. The reproducibility over a period of 1 month (n = 42) for the mass bias-corrected Sn isotope ratios is in the range of 0.06-0.16 per mil (2 s), for all the ratios monitored.