Hazard assessment of silicone oils (polydimethylsiloxanes, PDMS) used in antifouling-/foul-release-products in the marine environment

Non-eroding silicone-based coatings can effectively reduce fouling of ship hulls and are an alternative to biocidal and heavy metal-based antifoulings. The products, whose formulations and make up are closely guarded proprietary knowledge, consist of a silicone resin matrix and may contain unbound silicone oils (1-10%). If these oils leach out, they can have impacts on marine environments: PDMS are persistent, adsorb to suspended particulate matter and may settle into sediment. If oil films build up on sediments, infiltration may inhibit pore water exchange. PDMS do not bioaccumulate in marine organisms and soluble fractions have low toxicity to aquatic and benthic organisms. At higher exposures, undissolved silicone oil films or droplets can cause physical-mechanic effects with trapping and suffocation of organisms. These 'new' effects are not covered by current assessment schemes. PDMS make the case that very low water solubility and bioavailability do not necessarily preclude damage to marine environments.     

Geology,stratigraphy and palaeoenvironmental evolution of the Stephanorhinus kirchbergensis-bearing Quaternary palaeolake(s) of Gorzów Wielkopolski (NW Poland,Central Europe)

The sedimentary succession exposed in the Gorzów Wielkopolski area includes Eemian Interglacial (MIS 5e) or Early Weichselian (MIS 5d–e) deposits. The sedimentary sequence has been the object of intense interdisciplinary study, which has resulted in the identification of at least two palaeolake horizons. Both yielded fossil remains of large mammals, alongside pollen and plant macrofossils. All these proxies have been used to reconstruct the environmental conditions prevailing at the time of deposition, as well as to define the geological context and the biochronological position of the fauna. Optically stimulated luminescence dating of the glaciofluvial layers of the GS3 succession to 123.6 ± 10.1 (below the lower palaeolake) and 72.0 ± 5.2 ka (above the upper palaeolake) indicate that the site formed during the Middle–Late Pleistocene (MIS 6 – MIS 5). Radiocarbon-dating of the lacustrine organic matter revealed a tight cluster of Middle Pleniglacial Period (MIS 3) ages in the range of ~41–32 ka cal bp (Hengelo – Denekamp Interstadials). Holocene organic layers have also been found, with ¹⁴C ages within a range of 4330–4280 cal bp (Neolithic). Pollen and plant macrofossil records, together with sedimentological and geochemical data, confirm the dating to the Eemian Interglacial.     

Stress-induced proton disorder in hydrous ringwoodite

We have measured in situ high-pressure IR absorption of synthetic hydrous (Mg_xFe_1−x)₂SiO₄ ringwoodites (x = 0.00 to 0.61) up to a maximum pressure of 30 GPa. In our study, we combined the megabar-type diamond-anvil cell (DAC) with conventional and synchrotron FTIR spectroscopy. The high-pressure measurements were performed in three different pressure-transmitting environments: (1) CsI powder, (2) cryogenically loaded liquid argon, and (3) cryogenically loaded liquid argon annealed at 8.6 GPa at temperature of 120°C before further pressure increase. Between 10 and 12 GPa, all the samples loaded with methods (1) and (2), independent on composition, showed a sudden disappearance of the prominent OH-stretching feature and simultaneous discontinuities and/or changes in the pressure dependence of lattice vibrations compared with spectra of samples loaded with method (3). In experiments performed with method (3) the OH-stretching vibrations as well as lattice vibrations could be observed up to 30 GPa and their pressure behavior (dν/dP) can well be described by linear fits. Molecular vibrations, such as the OH stretching, are sensitive to non-hydrostatic conditions, especially in minerals with highly symmetric structures. We interpret the disappearance of the OH bands using methods (1) and (2) as a stress-induced proton disordering in hydrous ringwoodite. Our results confirm that argon pressure medium produces strongly non-hydrostatic conditions comparable to CsI or KBr, if it is not thermally annealed at pressures above 8 GPa. Our results suggest that the transition observed in hydrous Mg-ringwoodite end member is not present in compositions containing Fe. By comparing the behavior of samples compressed in different environments, we suggest that sudden disappearance of the OH-stretching band in hydrous ringwoodite could be driven by deterioration of the quasi-hydrostatic stress condition instead of a pressure-induced effect.     

Phenological observations made by the I. R. Bohemian Patriotic�CEconomic Society, 1828�C1847

Drought forecasting is a critical component of drought risk management. Identification of effective predictors is a major component of forecasting models. Sea surface temperature (SST) and sea level pressure (SLP) are relevant predictors for short- to long-term drought forecasts. However, these datasets are captured globally within a cell-wise network. This paper describes an approach to locate the most effective cells of the SST and SLP datasets using data mining. They are then applied as input to an adaptive neurofuzzy inference system (ANFIS) model to forecast possible droughts 3, 6, and 9?months in advance. Tehran plain was selected as the study area, and drought events are designated using the effective drought index (EDI). In another treatment, past values of the EDI time series were introduced to the ANFIS and the results compared with the previous findings. It was shown that R ² values were higher for all cases applying the SST/SLP datasets. Additionally, the performance of SST/SLP datasets and the ANFIS model was assessed according to ??drought?? or ??wet?? classification, and it was concluded that more than 90% of the time the ANFIS model detected the drought status correctly or with only a one class error.     

Ethnic politics and ambivalent imaginaries of the future at the Melaka Straits

This article examines the ambivalent relationship between members of the Portuguese-Melakan Kristang minority and the state from the 1940s to the present day through the lens of ethnic politics. It reveals how ambivalent imaginaries of the future have shaped the politics of community members and what strategies they have used to assert their place. Moreover, it analyses how partly contradictory, partly converging imaginaries of the future of the Melaka coastline fuelled the failure of the Melaka Gateway land reclamation project. Grounded in ethnographic fieldwork in Melaka in 2018 and 2019, it focuses on the Melaka Gateway, a large-scale land reclamation project located in the Melaka Straits where three man-made islands and one natural island with high-rise buildings, a cruise terminal and a deep sea port have been planned.     

Fossil fuel compounds from fly dust in recent organic matter of southern Poland peats

Several samples of peat from 6 bogs located in southern Poland were investigated for occurrence and distribution types of biomarkers present in their extractable organic matter fraction. It was found that there are inputs from two different sources of organic compounds differing in their characteristics and origin: (1) recent immature peat organic matter deposited in situ which is the source of all polar functionalized compounds, most of n-alkanes, and acyclic isoprenoids, and (2) mature fossil fuels, most probably bituminous coals from the Upper Silesia Coal Basin of vitrinite reflectance equivalent values of 0.9–1.1%. The latter compounds were most probably transported with fly ash to bogs from nearby settlements utilizing such fuel in domestic ovens. This group includes pentacyclic triterpenoids (hopanes and moretanes), minor amounts of n-alkanes, and numerous alkyl naphthalenes and alkyl phenanthrenes. All these compounds show distributions and values of geochemical ratios characteristic for mature organic matter confirming there ex situ origin.     

Polarized electronic absorption spectra of colourless chalcocyanite,CuSO4, with a survey on crystal fields in Cu2+ minerals

Polarized electronic absorption spectra of colourless chalcocyanite, CuSO₄, have been measured using microscope-spectrometric techniques. The spectra are characterized by a structured and clearly polarized band system in the near-infrared spectral range with components centred at 11,720, 10,545, 9,100, and 7,320 cm^?1, which have been assigned to crystal field d–d transitions of Cu²⁺ cations in pseudo-tetragonally elongated CuO₆ polyhedra with point symmetry C _i ( \(\bar{1}\) ). The polarization behaviour is interpreted based on a D ₂(C ₂″) pseudo-symmetry. Crystal field calculations were performed for the actual triclinic point symmetry by applying the Superposition Model of crystal fields, as well as in terms of a ‘classic’ pseudo-tetragonal crystal field approach yielding the parameters Dq _(eq) = 910, Dt = 395, and Ds = 1,336 cm^?1, corresponding to a cubically averaged Dq _cub = 679 cm^?1. A comparative survey on crystal fields in Cu²⁺ minerals shows that the low overall crystal field strength in chalcocyanite, combined with a comparatively weak pseudo-tetragonal splitting of energy levels, is responsible for its unique colourless appearance among oxygen-based Cu²⁺ minerals. The weak crystal field in CuSO₄ can be related to the lower position of the SO₄ ^2? anion compared to, e.g. the H₂O molecule in the spectrochemical series of ligands.     

Formation of methane in comet impacts: implications for Earth, Mars, and Titan

We calculate the amount of methane that may form via reactions catalyzed by metal-rich dust that condenses in the wake of large cometary impacts. Previous models of the gas-phase chemistry of impacts predicted that the terrestrial planets' atmospheres should be initially dominated by CO/CO₂, N₂, and H₂O. CH₄ was not predicted to form in impacts because gas-phase reactions in the explosion quench at temperatures ∼2000 K, at which point all of the carbon is locked in CO. We argue that the dust that condenses out in the wake of a large comet impact is likely to have very effective catalytic properties, opening up reaction pathways to convert CO and H₂ to CH₄ and CO₂, at temperatures of a few hundred K. Together with CO₂, CH₄ is an important greenhouse gas that has been invoked to compensate for the lower luminosity of the Sun ∼4 Gyr ago. Here, we show that heterogeneous (gas-solid) reactions on freshly-recondensed dust in the impact cloud may provide a plausible nonbiological mechanism for reducing CO to CH₄ before and during the emergence of life on Earth, and perhaps Mars as well. These encouraging results emphasize the importance of future research into the kinetics and catalytic properties of astrophysical condensates or “smokes” and also more detailed models to determine the conditions in impact-generated dust clouds.     

The Ecology of a Novel Symbiosis Between a Marine Peritrich Ciliate and Chemoautotrophic Bacteria

Abstract. A symbiosis between a sessile colonial ciliate, Zoothamnium niveum HEMPRICH & EHRENBERG. 1831. and chemolithoautotrophic bacteria oxidizing reduced sulfur compounds is described. The ciliates and their ectosymbionts occur on mangrove peat in the Caribbean. The feather-shaped ciliate colonies expand and contract, thus exposing the microbes alternately to oxygenated water above and sulfidic water within the boundary layer developed on the surface of the highly sulfidic peat. The symbioticciliates colonize sites with high sulfide flux where the microbial surface mat has been disturbed and grow there until the microbe mat re-establishes itself.     

Hydroxyl in mantle olivine xenocrysts from the Udachnaya kimberlite pipe

The incorporation of hydrogen in mantle olivine xenocrysts from the Udachnaya kimberlite pipe was investigated by Fourier-transform infrared spectroscopy and secondary ion mass spectrometry (SIMS). IR spectra were collected in the OH stretching region on oriented single crystals using a conventional IR source at ambient conditions and in situ at temperatures down to −180°C as well as with IR synchrotron radiation. The IR spectra of the samples are complex containing more than 20 strongly polarized OH bands in the range 3,730–3,330 cm⁻¹. Bands at high energies (3,730–3,670 cm⁻¹) were assigned to inclusions of serpentine, talc and the 10 Å phase. All other bands are believed to be intrinsic to olivine. The corresponding point defects are (a) associated with vacant Si sites (3,607 cm⁻¹ E || a, 3,597 E || a, 3,571 cm⁻¹ E || c, 3,567 E || c, and 3,556 E || b), and (b) with vacant M1 sites (most of the bands polarized parallel to a). From the pleochroic behavior and position of the OH bands associated with the vacant M1 sites, we propose two types of hydrogen—one bonded to O1 and another to O2, so that both OH vectors are strongly aligned parallel to a. The O2–H groups may be responsible for the OH bands at higher wavenumbers than those for the O1–H groups. The multiplicity of the corresponding OH bands in the spectra can be explained by different chemical environments and by slightly different distortions of the M1 sites in these high-pressure olivines. Four samples were investigated by SIMS. The calculated integral molar absorption coefficient using the IR and SIMS results of 37,500±5,000 L mol H₂O cm⁻² is within the uncertainties slightly higher than the value determined by Bell et al. (J Geophys Res 108(B2):2105–2113, 2003) (28,450±1,830 L mol H₂O cm⁻²). The reason for the difference is the different distributions of the absorption intensity of the spectra of both studies (mean wavenumber 3,548 vs. 3,570 cm⁻¹). Olivine samples with a mean wavenumber of about 3,548 cm⁻¹ should be quantified with the absorption coefficient as determined in this study; those containing more bands at higher wavenumber (mean wavenumber 3,570 cm⁻¹) should be quantified using the value determined by Bell et al. (J Geophys Res 108(B2):2105–2113, 2003).