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Whillans Subglacial Lake (SLW) lies beneath 801 m of ice in the lower portion of the Whillans Ice Stream (WIS) in West Antarctica and is part of an extensive and active subglacial drainage network. Here, the geochemical characterization of SLW rare earth elements (REE), trace elements (TE), free amino acids (FAA), and phenolic compounds (PC) measured in lakewater and sediment porewater are reported. The results show, on average, higher values of REEs in the lakewater than in the porewater, and clear changes in all REE concentrations and select redox sensitive trace element concentrations in porewaters at a depth of ~15 cm in the 38 cm lake sediment core. This is consistent with prior results on the lake sediment redox conditions based on gas chemistry and microbiological data. Low concentrations of vanillyl phenols were measured in the SLW water column with higher concentrations in porewater samples and their concentration profiles in the sediments may also reflect changing redox conditions in the sediments. Vanillin concentrations increased with depth in the sediments as oxygenation decreases, while the concentrations of vanillic acid, the more oxidized component, were higher in the more oxygenated surface sediments. Collectively these results indicate redox changes occurring with the upper 38 cm of sediment in SLW and provide support for the existence of a seawater source, already hypothesized, in the sediments below the lowest measured depth, and of a complex and dynamic geochemical system beneath the West Antarctic Ice Sheet. Our results are the first to detail geochemical properties from an Antarctic subglacial environment using direct sampling technology. Due to their isolation from the wider environment, subglacial lakes represent one of our planets last pristine environments that provide habitats for microbial life and natural biogeochemical cycles but also impact the basal hydrology and can cause ice flow variations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Fe(II) is more soluble and bioavailable than Fe(III) species, therefore the investigation of their relative abundance and redox processes is relevant to better assess the supply of bioavailable iron to the ocean and its impact on marine productivity. In this context, we present a discrete chemiluminescence-based method for the determination of Fe(II) in firn matrices. The method was applied on discrete samples from a snow pit collected at Dome C (DC, Antarctica) and on a shallow firn core from the Holtedahlfonna glacier (HDF, Svalbard), providing the first Fe(II) record from both Antarctica and Svalbard. The method showed low detection limits (0.006 ng g -1 for DC and 0.003 ng g -1 for the HDF) and a precision ranging from 3% to 20% RSD. Fe(II) concentrations ranged between the LoD and 0.077 ng g -1 and between the LoD and 0.300 ng g -1 for the Antarctic and Arctic samples, respectively. The Fe(II) contribution with respect to the total dissolved Fe was comparable in both sites accounting, on average, for 5% and 3%, respectively. We found that Fe(II) correctly identified the Pinatubo/Cerro Hudson eruption in the DC record, demonstrating its reliability as volcanic tracer, while, on the HDF core, we provided the first preliminary insight on the processes that might influence Fe speciation in firn matrices (i.e. organic ligands and pH influences)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

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.

Lead (Pb), cadmium (Cd), copper (Cu) and zinc (Zn) have been measured by electrothermal atomic absorption spectrometry in various sections of the 3623 m deep ice core drilled at Vostok, in central East Antarctica. The sections were dated from 240 to 410 kyear BP (Marine Isotopic Stages (MIS) 7.5 to 11.3), which corresponds to the 3rd and 4th glacial-interglacial cycles before present. Concentrations are found to have varied greatly during this 170 kyear time period, with high concentration values during the coldest climatic stages such as MIS 8.4 and 10.2 and much lower concentration values during warmer periods, such as the interglacials MIS 7.5, 9.3 and 11.3. Rock and soil dust were the dominant sources for Pb, whatever the period, and for Zn and Cu and possibly Cd during cold climatic stages. The contribution from volcanic emissions was important for Cd during all periods and might have been significant for Cu and Zn during warm periods.

The more important water masses generated by the interaction of Circumpolar Deep Water and the shelf waters in the western sector of the Ross Sea are characterized for trace element contents. The distribution of cadmium, lead, copper, zinc, iron, manganese and chromium during the austral summer is analysed and discussed according to the physical, chemical and biological processes which affect the composition of the water masses. The Cd concentration is found to have a relative high variability that can be related to biological activity and the water mass age, MCDW presents a mean dissolved concentration (SD) of 0.77 (0.07) nmol kg(-1), while the HSSW and AASW have a mean concentration of 0.63 (0.06) and 0.61 (0.16) nmol kg(-1), respectively. Lead features the typical distribution of a scavenged element with a surface maximum ranging between 22 and 130 pmol kg(-1) decreasing to 11 pmol kg(-1) in deep waters. However, the vertical distribution in the shelf area features a maximum concentration in intermediate/deep waters and we can hypothesize that the distribution may be influenced by more than one source. The surface dissolved concentration of zinc and copper were un-homogeneously distributed, the mean (SD) values were 5.25 (2.92) and 1.99 (1.49) nmol kg(-1) for zinc and copper, respectively and increased with depth for both the elements. We may therefore hypothesize enrichment in the dissolved phase deriving from recycling in deep waters. 95% of the chromium was in dissolved form and showed a superficial depletion; the mean concentrations were 1.6 +/- 0.2 and 2.6 +/- 0.8 nmol kg(-1) for surface and deep waters respectively. The vertical distribution of dissolved manganese was quite homogeneous with a mean concentration 0.96 +/- 0.7 nmol kg(-1). The particulate iron and manganese concentration trends are similar and feature a significant bottom increase implying a significant input from resuspension; the mean concentration of particulate ranged between 1.4 and 7.4 nmol kg(-1) for iron and ranged between 0.072 and 0.29 nmol kg(-1) for manganese.

Atmospheric particulate with an aerodynamic diameter <10 microm (PM10) was sampled continuously during the austral summers of 2000-2001 and 2001-2002 at a coastal site near to the Italian base of Terra Nova, Antarctica. Li, Pb, Cd, U, Ba, Bi, Cs, Rb, Tl, Sr, Al, V, Fe, Cu, Mn, Zn, Co, Ag were determined by inductively coupled sector field mass spectroscopy (ICP-SFMS) after sample digestion by a combination of HF, HNO3, and H2O2 in ultraclean conditions. Quality control of the analytical procedure was carried out by blank control, by evaluating the limits of detection, recoveries and repeatability. Concentrations found are extremely low for most metals, confirming the high purity of Antarctic aerosol. Principal Component Analysis (PCA) highlights high correlations among Pb, Cr, Bi, Cu and Zn concentration values and among Li, U, Ba, Cs, Rb, Al, V, Fe, Mn, Co concentration values permitting the identification of two principal source groups, namely crustal dust and human emission activities. Elements of anthropogenic origins (Pb, Cr, Cu, Zn) were highly enriched with respect to their crustal composition.

Direct and simultaneous determination of Al, Ag, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Pb, Sb, U, V and Zn in diluted (1:10 v:v) seawater from the Antarctic Ocean and the Venice Lagoon at the ng mL(-1) and pg mL(-1) level has been performed by using an inductively coupled plasma sector field mass spectrometer (ICP-SFMS). Samples were analysed by using a PFA microflow nebulizer coupled with a desolvation system or a PFA microflow nebulizer coupled with a Teflon spray chamber, respectively. Measurements were carried out at low (LR, m/Delta m=300), medium (MR, m/Delta m=3,000) and high (HR, m/Delta m=7,500) resolutions depending on the studied isotope. To avoid contamination, sample pre-treatment was carried out in a clean laboratory equipped with a Class 100 vertical laminar flow hood. Concentration ranges (minimum-maximum in ng mL(-1)) found in the Antarctic seawater samples (in depth profiles) were: Ag 0.0004-0.0018, As 0.69-1.32, Cd 0.031-0.096, Co 0.018-0.065, Cr 0.18-0.46, Cu 0.04-1.58, Fe 0.13-1.63, Mn 0.02-0.12, Mo 5.97-12.46, Pb 0.007-0.074, Sb 0.033-0.088, U 0.5-1.9, V 0.6-2.5 and Zn 0.16-0.80. Concentration ranges (min-max in ng mL(-1)) found in the Venice Lagoon water samples (temporal profile from a benthic chamber experiment) were: Al 0.24-0.61, Ag 0.007-0.031, As 1.42-2.27, Cd 0.050-0.182, Co 0.440-1.461, Cr 0.15-0.34, Cu 0.81-2.46, Fe 0.25-1.66, Mn 11.6-31.7, Mo 6.50-10.6, Pb 0.047-0.225, Sb 0.240-0.492, U 1.7-3.3, V 1.3-2.8 and Zn 5.20-21.5. The detection limits range between 0.06 pg mL(-1) for Ag and U to 15 pg mL(-1) for Fe. In order to check the accuracy of the analytical procedure, measurements of the trace elements in a certified reference material (coastal Atlantic seawater, CASS-4-NRCC) were compared with the certified values. In addition, the results from the Antarctic and Venice Lagoon samples were compared with those obtained by using different analytical techniques.