Anthropogenic debris in three sympatric seal species of the Western Antarctic Peninsula.

Litter pollution is a growing concern, including for Antarctica and the species that inhabit this ecosystem. In this study, we investigated the microplastic contamination in three seal species that inhabit the Western Antarctic Peninsula: crabeater (Lobodon carcinophaga), leopard (Hydrurga leptonyx) and Weddell (Leptonychotes weddellii) seals. Given the worldwide ubiquity of this type of contaminant, including the Southern Ocean, we hypothesized that the three seal species would present anthropogenic debris in their feces. We examined 29 scat samples of crabeater (n = 5), leopard (n = 13) and Weddell (n = 11) seals. The chemical composition of the items found were identified using micro-Raman and micro-FTIR spectroscopies. All the samples of the three species presented anthropic particles (frequency of occurrence - %FO - 100 %). Fibers were the predominant debris, but fragments and filaments were also present. Particles smaller than 5 mm (micro debris) were predominant in all the samples. Leopard seals ingested significantly larger micro-debris in comparison with the other seal species. The dominant color was black followed by blue and white. Micro-Raman and micro-FTIR Spectroscopies revealed the presence of different anthropogenic pigments such as reactive blue 238, Indigo 3600 and copper phthalocyanine (blue and green). Carbon black was also detected in the samples, as well as plastic polymers such as polystyrene, polyester and polyethylene terephthalate (PET), polyamide, polypropylene and polyurethane These results confirm the presence of anthropogenic contamination in Antarctic seals and highlight the need for actions to mitigate the effects and reduce the contribution of debris in the Antarctic ecosystem.

Microplastics and anthropogenic debris in rainwater from Bahia Blanca, Argentina.

Concern about atmospheric microplastic (MP) contamination has increased in recent years. This study assessed the abundance of airborne anthropogenic particles, including MPs, deposited in rainfall in Bahia Blanca, southwest Buenos Aires, Argentina. Rainwater samples were collected monthly from March to December 2021 using an active wet-only collector consisting of a glass funnel and a PVC pipe that is only open during rain events. Results obtained show that all rain samples contained anthropogenic debris. The term "anthropogenic debris" is used to refer to the total number of particles as not all the particles found could be determined as plastic. Among all the samples, an average deposition of 77 ± 29 items (anthropogenic debris) m-2d-1 was found. The highest deposition was observed in November (148 items m-2d-1) while the lowest was found in March (46 items m-2d-1). Anthropogenic debris ranged in size from 0.1 mm to 3.87 mm with the most abundant particles being smaller than 1 mm (77.8%). The dominant form of particles found were fibers (95%), followed by fragments (3.1%). Blue color predominated (37.2%) in the total number of samples, followed by light blue (23.3%) and black (21.7%). Further, small particles (<2 mm), apparently composed of mineral material and plastic fibers, were recognized. The chemical composition of suspected MPs was examined by Raman microscopy. The analysis of µ-Raman spectra confirmed the presence of polystyrene, polyethylene terephthalate, and polyethylene vinyl acetate fibers and provided evidence of fibers containing industrial additives such as indigo dye. This is the first assessment of MP pollution in rain in Argentina.

Beached microplastics at the Bahia Blanca Estuary (Argentina): Plastic pellets as potential vectors of environmental pollution by POPs.

Microplastics (MPs) from the coastal areas of a highly anthropised estuary were sampled to assess their distribution in coastal sediments and their role as potential vectors of pollution. The average MP density was 1693 ± 2315 MPs/kg, which mainly accumulated in the high tide and storm berm areas of the beach. The Microplastic Pollution Index (MPPI), Microplastic Impact Coefficient (CMPI), Hierarchical Cluster Analysis and Principal Component Analysis revealed spatial variation in MPs pollution. High-density polyethylene plastic pellets were abundant at two beaches (192 ± 218 MPs/kg sediment). Furthermore, the presence of sorbed chemicals on pellets was assessed through GC-MS, showing 0.95 ± 0.09 ng/g of ∑7OCPs, 4.03 ± 0.89 ng/g of ∑7PCBs, 108.76 ± 12.88 ng/g of ∑16 PAHs and 122.79 ± 11.13 g/g of ∑29 PAHs. The sorption capacity of plastics, combined with their abundance, poses an environmental concern and also highlights their suitability as indicators of chemical exposure.

First assessment of debris pollution in the gastrointestinal content of juvenile Magellanic penguins (Spheniscus magellanicus) stranded on the west south Atlantic coasts.

This paper provides the first evidence of debris pollution, including plastic, in juvenile Magellanic penguins (Spheniscus magellanicus) found stranded on the Atlantic coast of southern Buenos Aires Province, Argentina. Macro-, meso- and microparticles of anthropogenic origin were observed in 100 % of the studied birds, with debris abundance ranging between 33 and 200 items/bird. Microparticles represented 91 % of the total debris and 97 % of them were fibers. Black particles were the most abundant (30 %), followed by transparent (26 %), blue (14 %), yellow (10.3 %), and red (10 %). Infrared and Raman spectroscopy identified 62.7 % of the total particles as plastics, with polypropylene (27.8 %) and polyester (21.6 %) being the most abundant polymers. Semi-synthetic cellulosic fibers, metallic particles, and pigments were also found. The presence of metallic microparticles was suggested for the first time in penguins. Stranded juvenile Magellanic penguins are proposed as promising bioindicators of plastic pollution in the South Atlantic.

Formation of HCO+ and HCS+ Ions in the Photodissociation of CH3OC(S)SCH3 under VUV Synchrotron Radiation.

Synchrotron-based total ion yield and photoelectron-photoion-coincidence spectra have been applied to investigate the electronic structure and the dissociative ionization of gaseous O,S-dimethyl xanthate, CH3OC(S)SCH3, in the shallow-core S 2p region. The spectral assignment and the electronic structure are interpreted in terms of the most stable synperiplanar conformer in the Cs symmetry point group. The use of tunable synchrotron radiation allows for a selective excitation of sulfur atoms at different photon energy values, including resonance transitions and ionization around the S 2p level. The fragmentation patterns show that the title molecule is well suited as a laboratory precursor of ionic species found in the interstellar medium, especially formyl and thioformyl cations, HCO+ and HCS+, respectively.

Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group's Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl3SCN and CCl2FSCN.

Both photoelectron spectroscopy (PES) data and PhotoElectron-PhotoIon-Coincidence (PEPICO) spectra obtained from a synchrotron facility have been used to examine the electronic structure and the dissociative ionization of halomethyl thiocyantes in the valence and shallow-core S 2p and Cl 2p regions. Two simple and closely related molecules, namely, CCl3SCN and CCl2FSCN, have been analyzed to assess the role of halogen substitution in the electronic properties of thiocyanates. The assignment of the He(I) photoelectron spectra has been achieved with the help of quantum chemical calculations at the outer-valence Green's function (OVGF) level of approximation. The first ionization energies observed at 10.55 and 10.78 eV for CCl3SCN and CCl2FSCN, respectively, are assigned to ionization processes from the sulfur lone pair orbital [n(S)]. When these molecules are compared with CX3SCN (X = H, Cl, F) species, a linear relationship between the vertical first ionization energy and electronegativity of CX3 group is observed. Irradiation of CCl3SCN and CCl2FSCN with photons in the valence energy regions leads to the formation of CCl2X+ and CClXSCN+ ions (X = Cl or F). Additionally, the achievement of the fragmentation patterns and the total ion yield spectra obtained from the PEPICO data in the S 2p and Cl 2p regions and several dissociation channels can be inferred for the core-excited species by using the triple coincidence PEPIPICO (PhotoElectron-PhotoIon-PhotoIon-Coincidence) spectra.

Structures of Trichloromethyl Thiocyanate, CCl3 SCN, in Gaseous and Crystalline State.

Trichloromethyl thiocyanate, CCl3 SCN, was structurally studied in both the gas and crystal phases by means of gas electron diffraction (GED) and single-crystal X-ray diffraction (XRD), respectively. Both experimental studies and quantum chemical calculations indicate a staggered orientation of the CCl3 group relative to the SCN group. This conclusion is supported by the similarity of the C-SCN bond length to that of the anti-structure of CH2 ClSCN (Berrueta Martínez et al. Phys. Chem. Chem. Phys. 2015, 17, 15805-15812). Bond lengths and angles are similar for gas and crystal CCl3 SCN structures; however, the crystal structure presents different intermolecular interactions. These include halogen and chalcogen type interactions, the geometry of which was studied. Characteristic C-Y⋅⋅⋅N angles (Y=Cl or S) close to 180° provide evidence for typical σ-hole interactions along the halogen/chalcogen-carbon bond in N⋅⋅⋅Cl and N⋅⋅⋅S, intermolecular units.

Photoelectron Spectroscopy and Ionic Fragmentation of OSeCl2 and Its Analogue OSCl2 under VUV Irradiation.

The electronic structure and the dissociative ionization of selenium oxychloride, OSeCl2, have been investigated in the valence region by using results from both photoelectron spectroscopy (PES) and synchrotron-based photoelectron photoion coincidence (PEPICO) spectra. The PES is assigned with the help of quantum chemical calculations at the outer-valence Green's function (OVGF) and symmetry adapted cluster/configuration interaction (SAC-CI) levels. The first energy ionization is observed at 11.47 eV assigned to the ionization of electrons formally delocalized over the Se, Cl, and O lone pair orbitals. Irradiation of OSeCl2 with photons in the valence region leads to the formation of OSeCl2(•+), OSeCl(+), SeCl2(•+), SeCl(+), and SeO(•+) ions. Furthermore, the inner shell Se 3p, Cl 2p, and Se 3s electronic regions of OSeCl2 together with S 2p, Cl 2p, and S 2s electronic regions of thionyl chloride, OSCl2, have been studied by using tunable synchrotron radiation. Thus, total ion yield spectra and the fragmentation patterns deduced from PEPICO spectra at the various excitation energies have been studied. Cl(+), O(•+), and Se(•+) ions appear as the most intense fragments in the OSeCl2 PEPICO spectra, like in the sulfur analogue OSCl2, whose photofragmentation is dominated by the Cl(+), O(•+), and S(•+) ions. Fragmentation processes in OSCl2 leading to the formation of the double coincidences involving atomic ions appear as the most intense in the PEPIPICO spectra.

Matrix isolation study of the conformations and photochemistry of S-ethyl fluorothioformate, FC(O)SCH2CH3.

The IR spectra of S-ethyl fluorothioformate, FC(O)SCH2CH3, were recorded in the vapor phase and compared with the Raman spectrum in the liquid state. Additional IR spectra of the compound isolated in argon and nitrogen matrices at ca. 12 K were also recorded. The title compound exhibits rich conformational equilibria at room temperature being C1 the most stable symmetry with a synperiplanar orientation of the carbonyl double bond (C═O) with respect to the S-C(sp(3)) single bond, while the C-C bond of the ethyl group presents a gauche orientation with respect to the C-S single bond. Several bands assigned to a second conformer were also observed in the IR matrix spectra. This second rotamer presents a planar skeleton (Cs point group) retaining the prevalent syn orientation of the FC(O)SCH2CH3 molecule with an antiperiplanar orientation of the C-C bond of the ethyl group with respect to the C-S bond. The variation of the nozzle temperature before matrix gas deposition gives rise to different conformer ratios. With these data an enthalpy difference of 0.45 kcal mol(-1) can be calculated between the more stable C1 and the Cs conformers. A third form, corresponding to the anti-gauche conformer, is also detected when the matrix is exposed to broad-band UV-visible irradiation. Moreover, the photochemistry of the Ar and N2 matrix-isolated species is studied. Conformational interconversion is observed at short irradiation times, whereas a decarbonylation process with the concomitant formation of a HC(S)CH3:HF molecular complex dominates the photochemistry of FC(O)SCH2CH3 of longer irradiation times. The new ethyl fluoro sulfide, FSCH2CH3, is proposed as an intermediate species.

Electronic properties of FC(O)SCH2CH3. a combined helium(I) photoelectron spectroscopy and synchrotron radiation study.

The valence electronic properties of S-ethyl flouromethanethioate (S-ethyl fluoromethsanethioate), FC(O)SCH2CH3, were investigated by means of He(I) photoelectron spectroscopy in conjunction with the analysis of the photofragmentation products determined by PEPICO (phtoelectron-photoion-coincidence) by using synchrotron radiation in the 11.1-21.6 eV photon energy range. The first band observed at 10.28 eV in the HeI photoelectron spectrum can be assigned with confidence to the ionization process from the HOMO [nπ(S) orbital], which is described as a lone pair formally localized on the sulfur atom, in agreement with quantum chemical calculations using the outer valence Green function method [OVGF/6-311++G (d,p)]. One of the most important fragmentation channels also observed in the valence region corresponds to the decarbonylation process yielding the [M-CO](·+) ion, which is clearly observed at m/z = 80. Moreover, S 2p and S 2s absorption edges have been examined by measuring the total ion yield spectra in the 160-240 eV region using variable synchrotron radiation. The dynamic of ionic fragmentation following the Auger electronic decay has been evaluated with the help of the PEPIPICO (photoion-photoion-photoelectron-coincidence spectra) technique.

Electronic properties and dissociative photoionization of thiocyanates. Part II. Valence and shallow-core (sulfur and chlorine 2p) regions of chloromethyl thiocyanate, CH2ClSCN.

A combination of photoelectron spectroscopy and synchrotron based photoelectron photoion coincidence (PEPICO) spectra has been applied to investigate the electronic structure and the dissociative ionization of the CH(2)ClSCN molecule in the valence region. The PES is assigned with the electronic structure calculations at the outer-valence Green's function and symmetry adapted cluster/configuration interaction (SAC-CI) levels offer an explanation of our experimental results. Upon vacuum ultraviolet irradiation the low-lying radical cation, located at 10.39 eV is formed. The molecular ion is observed in the time-of-flight mass spectra, together with the CH(2)SCN(+) and CH(2)Cl(+) daughter ions. The total ion yield spectra have been measured in the S 2p and Cl 2p regions and several channels have been determined in dissociative photoionization events for the core-excited species. Thus, by using time-of-flight mass spectrometry and synchrotron radiation the relative abundances of the ionic fragments and their kinetic energy release values were obtained from both PEPICO and photoelectron photoion photoion coincidence spectra. Possible fragmentation processes are discussed and compared with that found for the related CH(3)SCN species.