Biofilm Harvesters in Coastal Settings of the Early Palaeozoic

The ichnogenera Syringomorpha and Daedalus are here interpreted as products of infaunal biofilm harvesters. This study investigated: (1) Syringomorpha nilssoni and Syringomorpha isp. from the Cambrian Series 2‐Miaolingian Campanario Formation, northwest Argentina; and (2) Daedalus halli from the Floian Grès et Schistes de la Cluse de l’Orb Formation, Montagne Noire, France. Syringomorpha nilssoni occurs in sandy to mixed intertidal to lower shoreface deposits, whereas Syringomorpha isp. in the lower intertidal zone. Daedalus halli occurs in a lagoon and intertidal to lower shoreface sands of a barrier island. Syringomorpha and Daedalus comprise a vertical J‐shaped causative burrow and deep spreite. These ichnotaxa form monospecific assemblages (bioturbation index BI = 3–5) in quartzose medium‐ to fine‐grained sandstone, recording colonization in high‐energy tide‐and wave‐dominated settings. Lower abundances (BI = 1–2) are observed in silty sandstone. The abundance of both ichnogenera in mature sandstone is inconsistent with a classic deposit‐feeding strategy because ‘clean’ sediments are commonly impoverished of organic detritus, this being particularly true in Cambro‐Ordovician littoral settings lacking terrestrial plant detritus. Based on morphology, host sediment properties and comparison with modern structures, such those produced on intertidal and shallow subtidal setting by Arenicola marina and Paraonis fulgens, it is suggested that the diet of Syringomorpha and Daedalus producers may have consisted of biofilms colonising sand grains, associated eukaryotic microbes, and possibly meiofauna. Whereas Syringomorpha is a product of the Cambrian explosion, Daedalus is associated with the Ordovician Radiation. In contrast to most ichnotaxa, which display long temporal ranges, these two ichnogenera are restricted to the Cambrian and Ordovician‐Silurian, respectively. The underlying reasons for the relatively restricted stratigraphic ranges of these ichnotaxa are unclear, but space competition, and increased predation pressure may have played a role. The feeding strategy of the Daedalus and Syringomorpha producers was less efficient than suspension feeding and passive predation, trophic types epitomized by the dominant macroinfauna that persisted in water‐agitated nearshore sands during the rest of the Phanerozoic

Early diagenesis of redox-sensitive trace metals in the Peru upwelling area – Response to ENSO-related oxygen fluctuations in the water column

Pore water and solid phase data for redox-sensitive metals (Mn, Fe, V, Mo and U) were collected on a transect across the Peru upwelling area (11°S) at water depths between 78 and 2025 m and bottom water oxygen concentrations ranging from ~0 to 93 µM. By comparing authigenic mass accumulation rates and diffusive benthic fluxes, we evaluate the respective mechanisms of trace metal accumulation, retention and remobilization across the oxygen minimum zone (OMZ) and with respect to oxygen fluctuations in the water column related to the El Nino Southern Oscillation (ENSO). Sediments within the permanent OMZ are characterized by diffusive uptake and authigenic fixation of U, V and Mo as well as diffusive loss of Mn and Fe across the benthic boundary. Some of the dissolved Mn and Fe in the water column re-precipitate at the oxycline and shuttle particle-reactive trace metals to the sediment surface at the lower and upper boundary of the OMZ. At the lower boundary, pore waters are not sufficiently sulfidic as to enable an efficient authigenic V and Mo fixation. As a consequence, sediments below the OMZ are preferentially enriched in U which is delivered via both in situ pre-cipitation and lateral supply of U-rich phosphorites from further upslope. Trace metal cycling on the Peruvian shelf is strongly affected by ENSO-related oxygen fluctuations in bottom water. During periods of shelf oxygenation, surface sediments receive particulate V and Mo with metal (oxyhydr)oxides that derive from both terrigenous sources and precipitation at the retreating oxycline. After the recurrence of anoxic conditions, metal (oxyhydr)oxides are reductively dissolved and the hereby liberated V and Mo are authigenically removed. This alternation between supply of particle-reactive trace metals during oxic periods and fixation during anoxic periods leads to a preferential accumulation of V and Mo compared to U on the Peruvian shelf. The decoupling of V, Mo and U accumulation is further accentuated by the varying susceptibility to re-oxidation of the different authigenic metal phases. While authigenic U and V are readily re-oxidized and recycled during periods of shelf oxygenation, the sequestration of Mo by authigenic pyrite is favored by the transient occurrence of oxidizing conditions.Our findings reveal that redox-sensitive trace metals respond in specific manner to short-term oxygen fluctuations in the water column. The relative enrichment patterns identified might be useful for the reconstruction of past OMZ extension and large-scale redox oscillations in the geological record

Microplastic Fragment and Fiber Contamination of Beach Sediments from Selected Sites in Virginia and North Carolina, USA

Microplastic particles (\u3c5 \u3emm) constitute a growing pollution problem within coastal environments. This study investigated the microplastic presence of estuarine and barrier island beaches in the states of Virginia and North Carolina, USA. Seventeen sediment cores were collected at four study sites and initially tested for microplastic presence by pyrolysis-gas chromatography–mass spectrometry. For the extraction, microplastic particles were first separated from the sediment using a high-density cesium chloride solution (1.88 g/mL). In a second step, an oil extraction collected the remaining microplastic particles of higher densities. Under the light microscope, the extracted microplastic particles were classified based on their morphologies into fragments and fibers. Raman microspectroscopy chemically identified a subset of microplastic particles as polypropylene, polyethylene terephthalate, poly(4-vinylbiphenyl), polystyrene, polyethylene, and nylon. The results show a concentration of microplastic particles (1410 ± 810 per kg of dry sediment) even in protected and ostensibly unpolluted estuarine and beach sediments of Virginia and North Carolina

Orthokeratinized Odontogenic Cyst of the Mandible with Heterotopic Cartilage

Cartilaginous metaplasia is a rare but well-documented phenomenon occurring in the wall of odontogenic keratocyst. The mural cartilage not associated with odontogenic keratocyst has been reported only once in a maxillary teratoid cyst of congenital origin to our knowledge. A case presented is a 38-year-old man with intraosseous keratinizing epidermoid cyst in the mandible, the wall of which contained a nodule of mature hyaline cartilage. The present lesion likely represents a previously undescribed, histologic hybrid consisting of orthokeratinized odontogenic cyst and cartilaginous heterotopia

Central odontogenic fibroma: a case report with long-term follow-up

An osteolytic tumour of the mandible with prominent expansive growth on the alveolar ridge and displacement of the involved teeth is described in a 28-year-old man. The lesion was diagnosed as a central odontogenic fibroma, an uncommon benign neoplasm derived from dental apparatus, and was removed by curettage. The patient remains asymptomatic after thirteen years of follow-up, which supports the claimed indolent behavior of this poorly documented disease and the adequacy of a conservative surgical treatment

Surface Morphologies in a Mars-Analog Ca-Sulfate Salar, High Andes, Northern Chile

Salar de Pajonales, a Ca-sulfate salt flat in the Chilean High Andes, showcases the type of polyextreme environment recognized as one of the best terrestrial analogs for early Mars because of its aridity, high solar irradiance, salinity, and oxidation. The surface of the salar represents a natural climate-transition experiment where contemporary lagoons transition into infrequently inundated areas, salt crusts, and lastly dry exposed paleoterraces. These surface features represent different evolutionary stages in the transition from previously wetter climatic conditions to much drier conditions today. These same stages closely mirror the climate transition on Mars from a wetter early Noachian to the Noachian/Hesperian. Salar de Pajonales thus provides a unique window into what the last near-surface oases for microbial life on Mars could have been like in hypersaline environments as the climate changed and water disappeared from the surface. Here we open that climatological window by evaluating the narrative recorded in the salar surface morphology and microenvironments and extrapolating to similar paleosettings on Mars. Our observations suggest a strong inter-dependence between small and large scale features that we interpret to be controlled by extrabasinal changes in environmental conditions, such as precipitation-evaporation-balance changes and thermal cycles, and most importantly, by internal processes, such as hydration/dehydration, efflorescence/deliquescence, and recrystallization brought about by physical and chemical processes related to changes in groundwater recharge and volcanic processes. Surface structures and textures record a history of hydrological changes that impact the mineralogy and volume of Ca-sulfate layers comprising most of the salar surface. Similar surface features on Mars, interpreted as products of freeze-thaw cycles, could, instead, be products of water-driven, volume changes in salt deposits. On Mars, surface manifestations of such salt-related processes would point to potential water sources. Because hygroscopic salts have been invoked as sources of localized, transient water sufficient to support terrestrial life, such structures might be good targets for biosignature exploration on Mars

Conjugation of a Ru(II) Arene Complex to Neomycin or to Guanidinoneomycin Leads to Compounds with Differential Cytotoxicities and Accumulation between Cancer and Normal Cells

A straightforward methodology for the synthesis of conjugates between a cytotoxic organometallic ruthenium(II) complex and amino- and guanidinoglycosides, as potential RNA-targeted anticancer compounds, is described. Under microwave irradiation, the imidazole ligand incorporated on the aminoglycoside moiety (neamine or neomycin) was found to replace one triphenylphosphine ligand from the ruthenium precursor [(η6-p-cym)RuCl(PPh3)2]+, allowing the assembly of the target conjugates. The guanidinylated analogue was easily prepared from the neomycin-ruthenium conjugate by reaction with N,N′-di-Boc-N″-triflylguanidine, a powerful guanidinylating reagent that was compatible with the integrity of the metal complex. All conjugates were purified by semipreparative high-performance liquid chromatography (HPLC) and characterized by electrospray ionization (ESI) and matrix-assisted laser desorption-ionization time-of-flight (MALDI-TOF) mass spectrometry (MS) and NMR spectroscopy. The cytotoxicity of the compounds was tested in MCF-7 (breast) and DU-145 (prostate) human cancer cells, as well as in the normal HEK293 (Human Embryonic Kidney) cell line, revealing a dependence on the nature of the glycoside moiety and the type of cell (cancer or healthy). Indeed, the neomycin-ruthenium conjugate (2) displayed moderate antiproliferative activity in both cancer cell lines (IC50 ≈ 80 μM), whereas the neamine conjugate (4) was inactive (IC50 ≈ 200 μM). However, the guanidinylated analogue of the neomycin-ruthenium conjugate (3) required much lower concentrations than the parent conjugate for equal effect (IC50 = 7.17 μM in DU-145 and IC50 = 11.33 μM in MCF-7). Although the same ranking in antiproliferative activity was found in the nontumorigenic cell line (3 2 > 4), IC50 values indicate that aminoglycoside-containing conjugates are about 2-fold more cytotoxic in normal cells (e.g., IC50 = 49.4 μM for 2) than in cancer cells, whereas an opposite tendency was found with the guanidinylated conjugate, since its cytotoxicity in the normal cell line (IC50 = 12.75 μM for 3) was similar or even lower than that found in MCF-7 and DU-145 cancer cell lines, respectively. Cell uptake studies performed by ICP-MS with conjugates 2 and 3 revealed that guanidinylation of the neomycin moiety had a positive effect on accumulation (about 3-fold higher in DU-145 and 4-fold higher in HEK293), which correlates well with the higher antiproliferative activity of 3. Interestingly, despite the slightly higher accumulation in the normal cell than in the cancer cell line (about 1.4-fold), guanidinoneomycin-ruthenium conjugate (3) was more cytotoxic to cancer cells (about 1.8-fold), whereas the opposite tendency applied for neomycin-ruthenium conjugate (2). Such differences in cytotoxic activity and cellular accumulation between cancer and normal cells open the way to the creation of more selective, less toxic anticancer metallodrugs by conjugating cytotoxic metal-based complexes such as ruthenium(II) arene derivatives to guanidinoglycosides

Organoiridium complexes : anticancer agents and catalysts

Iridium is a relatively rare precious heavy metal, only slightly less dense than osmium. Researchers have long recognized the catalytic properties of square-planar Ir(I) complexes, such as Crabtree's hydrogenation catalyst, an organometallic complex with cyclooctadiene, phosphane, and pyridine ligands. More recently, chemists have developed half-sandwich pseudo-octahedral pentamethylcyclopentadienyl Ir(III) complexes containing diamine ligands that efficiently catalyze transfer hydrogenation reactions of ketones and aldehydes in water using H2 or formate as the hydrogen source. Although sometimes assumed to be chemically inert, the reactivity of low-spin 5d(6) Ir(III) centers is highly dependent on the set of ligands. Cp* complexes with strong σ-donor C^C-chelating ligands can even stabilize Ir(IV) and catalyze the oxidation of water. In comparison with well developed Ir catalysts, Ir-based pharmaceuticals are still in their infancy. In this Account, we review recent developments in organoiridium complexes as both catalysts and anticancer agents. Initial studies of anticancer activity with organoiridium complexes focused on square-planar Ir(I) complexes because of their structural and electronic similarity to Pt(II) anticancer complexes such as cisplatin. Recently, researchers have studied half-sandwich Ir(III) anticancer complexes. These complexes with the formula [(Cp(x))Ir(L^L')Z](0/n+) (with Cp* or extended Cp* and L^L' = chelated C^N or N^N ligands) have a much greater potency (nanomolar) toward a range of cancer cells (especially leukemia, colon cancer, breast cancer, prostate cancer, and melanoma) than cisplatin. Their mechanism of action may involve both an attack on DNA and a perturbation of the redox status of cells. Some of these complexes can form Ir(III)-hydride complexes using coenzyme NAD(P)H as a source of hydride to catalyze the generation of H2 or the reduction of quinones to semiquinones. Intriguingly, relatively unreactive organoiridium complexes containing an imine as a monodentate ligand have prooxidant activity, which appears to involve catalytic hydride transfer to oxygen and the generation of hydrogen peroxide in cells. In addition, researchers have designed inert Ir(III) complexes as potent kinase inhibitors. Octahedral cyclometalated Ir(III) complexes not only serve as cell imaging agents, but can also inhibit tumor necrosis factor α, promote DNA oxidation, generate singlet oxygen when photoactivated, and exhibit good anticancer activity. Although relatively unexplored, organoiridium chemistry offers unique features that researchers can exploit to generate novel diagnostic agents and drugs with new mechanisms of action