Ostracods as ecological and isotopic indicators of lake water salinity changes: the Lake Van example

Ostracods are common lacustrine calcitic microfossils. Their faunal assemblage and morphological characteristics are important ecological proxies, and their valves are archives of geochemical information related to palaeoclimatic and palaeohydrological changes. In an attempt to assess ostracod ecology (taxonomic diversity and valve morphology) combined with valve geochemistry (δ18O and δ13C) as palaeosalinity indicators, we analysed sedimentary material from the International Continental Scientific Drilling Program (ICDP) Ahlat Ridge site from a terminal and alkaline lake, Lake Van (Turkey), covering the last 150&thinsp;kyr. Despite a low species diversity, the ostracod faunal assemblage reacted sensitively to changes in the concentration of total dissolved salts in their aquatic environment. Limnocythere inopinata is present throughout the studied interval, while Limnocythere sp. A is restricted to the Last Glacial period and related to increased lake water salinity and alkalinity. The presence of species belonging to the genus Candona is limited to periods of lower salinity. Valves of Limnocytherinae species (incl. L. inopinata) display nodes (hollow protrusions) during intervals of increased salinity. Both the number of noded valves and the number of nodes per valve appear to increase with rising salinity, suggesting that node formation is related to hydrological changes (salinity and/or alkalinity). In contrast to Lake Van's bulk δ18O record, the δ18O values of ostracod valves do record relative changes of the lake volume, with lower values during high lake level periods. The δ13C values of different species reflect ostracod habitat preferences (i.e. infaunal vs. epifaunal) but are less sensitive to hydrological changes. However, combined with other proxies, decreasing Holocene δ13C values may indicate a freshening of the lake water compared to the low lake level during the Last Glacial period. The Lake Van example underscores the significance and value of coupling ostracod ecology and valve geochemistry in palaeoenvironmental studies of endorheic lake basins.</p

Local and Regional Indian Summer Monsoon Precipitation Dynamics During Termination II and the Last Interglacial

To date Indian summer monsoon (ISM) dynamics have been assessed by changes in stalagmite δ18O. However, stalagmite δ18O is influenced by multiple environmental factors (e.g., atmospheric moisture transport, rainfall amount at the study site, and ISM seasonality), precluding simple and clear reconstructions of rainfall amount or variability. This study aims to disentangle these environmental factors by combining δ18O, δ44Ca, and elemental data from a stalagmite covering Termination II and the last interglacial from Mawmluh Cave, NE India, to produce a semiquantitative reconstruction of past ISM rainfall. We interpret δ18O as a mixed signal of rainfall source dynamics and rainfall amount and coupled δ44Ca and X/Ca ratios as indicators of local infiltration rate and prior calcite precipitation in the karst zone. The wettest conditions in our studied interval (135 and 100 kyrs BP; BP = before present, with the present being 1950 CE) occurred during Marine Isotope Stage 5e. Our multiproxy data set suggests a likely change in seasonal distribution of Marine Isotope Stage 5e rainfall compared to the Holocene; the wet season was longer with higher‐than‐modern dry season rainfall. Using the last interglacial as an analogue for future anthropogenic warming, our data suggest a more erratic ISM behavior in a warmer world

Syntheses, Characterization, Density Functional Theory Calculations, and Activity of Tridentate SNS Zinc Pincer Complexes Based on Bis-Imidazole or Bis-Triazole Precursors

A series of tridentate pincer ligands, each possessing two sulfur- and one nitrogen-donor functionalities (SNS), based on bis-imidazole or bis-triazole salts were metallated with ZnCl2 to give new tridentate SNS pincer zinc(II) complexes [(SNS)ZnCl]+. The zinc complexes serve as models for the zinc active site in liver alcohol dehydrogenase (LADH) and were characterized with single crystal X-ray diffraction, 1H, 13C, and HSQC NMR spectroscopies, electrospray mass spectrometry, and elemental analysis. The zinc complexes feature SNS donor atoms and pseudotetrahedral geometry about the zinc center, as is seen for liver alcohol dehydrogenase. The bond lengths and bond angles of the zinc complexes correlate well to those in horse LADH. The SNS ligand precursors were characterized with 1H, 13C, and HSQC NMR spectroscopies, elemental analysis, and cyclic voltammetry, and were found to be redox active. Gaussian calculations were performed and agree with the experimentally observed oxidation potentials for the pincer ligand precursors. The zinc complexes were screened for the reduction of electron-poor aldehydes in the presence of a hydrogen donor, 1-benzyl-1,4-dihydronicotinamide (BNAH), and it was determined that they enhance the reduction of electron-poor aldehydes. The SNS zinc pincer complexes with bis-triazole ligand precursors exhibit higher activity for the reduction of 4-nitrobenzaldehyde than do SNS zinc pincer complexes with bis-imidazole ligand precursors. Quantitative stoichiometric conversion was seen for the reduction of pyridine-2-carboxaldehyde via SNS zinc pincer complexes with either bis-imidazole or bis-triazole ligand precursors

Syntheses, characterization, density functional theory calculations, and activity of tridentate SNS zinc pincer complexes

A series of tridentate SNS ligand precursors were metallated with ZnCl2 to give new tridentate SNS pincer zinc complexes. The zinc complexes serve as models for the zinc active site in liver alcohol dehydrogenase (LADH) and were characterized with single crystal X-ray diffraction, 1H, 13C, and HSQC NMR spectroscopies and electrospray mass spectrometry. The bond lengths and bond angles of the zinc complexes correlate well to those in horse LADH. The zinc complexes feature SNS donor atoms and pseudotetrahedral geometry about the zinc center, as is seen for liver alcohol dehydrogenase. The SNS ligand precursors were characterized with 1H, 13C, and HSQC NMR spectroscopies and cyclic voltammetry, and were found to be redox active. Gaussian calculations were performed and agree quite well with the experimentally observed oxidation potential for the pincer ligand. The zinc complexes were screened for the reduction of electron poor aldehydes in the presence of a hydrogen donor, 1-benzyl-1,4-dihydronicotinamide (BNAH). The zinc complexes enhance the reduction of electron poor aldehydes. Density functional theory calculations were performed to better understand why the geometry about the zinc center is pseudo-tetrahedral rather than pseudo-square planar, which is seen for most pincer complexes. For the SNS tridentate pincer complexes, the data indicate that the pseudo-tetrahedral geometry was 43.8 kcal/mol more stable than the pseudo-square planar geometry. Density functional theory calculations were also performed on zinc complexes with monodentate ligands and the data indicate that the pseudo-tetrahedral geometry was 30.6 kcal/mol more stable than pseudo-square planar geometry. Overall, the relative stabilities of the pseudo-tetrahedral and pseudo-square planar systems are the same for this coordination environment whether the ligand set is a single tridentate SNS system or is broken into three separate units. The preference of a d10 Zn center to attain a tetrahedral local environment trumps any stabilization gained by removal of constraints within the ligand set

Ionometric sensor for ammonium ions control in sewage waters

Цель работы заключалась в создании измерительного датчика для автоматизированного потенциометрического контроля содержания ионов аммония в проточных условиях. В результате исследования разработана конструкция электрода сравнения измерительного датчика, представляющая собой ионоселективный электрод, опущенный в буферную систему с катионитом. В работе представлен потенциометрический анализ модельных растворов ионов аммония, изучено мешающее влияние температуры, а также определена стабильность предложенной системы. The purpose of the work was to create a sensor for automated potentiometric monitoring of the ammonium ions content in flowing conditions. As a result of the study, the reference electrode design was developed. This is an ion-selective electrode lowered into a buffer system with cation exchanger. The work presents a potentiometric analysis of ammonium ions model solutions, the study of temperature interfering effect, and system's stability determination

500,000 Years of Environmental History in Eastern Anatolia: The PALEOVAN Drilling Project

International Continental Scientific Drilling Program (ICDP) drilled a complete succession of the lacustrine sediment sequence deposited during the last ~500,000 years in Lake Van, Eastern Anatolia (Turkey). Based on a detailed seismic site survey, two sites at a water depth of up to 360 m were drilled in summer 2010, and cores were retrieved from sub-lake-floor depths of 140 m (Northern Basin) and 220 m (Ahlat Ridge). To obtain a complete sedimentary section, the two sites were multiple-cored in order to investigate the paleoclimate history of a sensitive semi-arid region between the Black, Caspian, and Mediterranean seas. Further scientific goals of the PALEOVAN project are the reconstruction of earthquake activity, as well as the temporal, spatial, and compositional evolution of volcanism as reflected in the deposition of tephra layers. The sediments host organic matter from different sources and hence composition, which will be unravelled using biomarkers. Pathways for migration of continental and mantle-derived noble gases will be analyzed in pore waters. Preliminary 40Ar/39Ar single crystal dating of tephra layers and pollen analyses suggest that the Ahlat Ridge record encompasses more than half a million years of paleoclimate and volcanic/geodynamic history, providing the longest continental record in the entire Near East to date

Clinical and molecular characterization of isolated M1 disease in pediatric medulloblastoma: experience from the German HIT-MED studies

PURPOSE: To evaluate the clinical impact of isolated spread of medulloblastoma cells into cerebrospinal fluid without additional macroscopic metastases (M1-only). METHODS: The HIT-MED database was searched for pediatric patients with M1-only medulloblastoma diagnosed from 2000 to 2019. Corresponding clinical and molecular data was evaluated. Treatment was stratified by age and changed over time for older patients. RESULTS: 70 patients with centrally reviewed M1-only disease were identified. Clinical data was available for all and molecular data for 45/70 cases. 91% were non-WNT/non-SHH medulloblastoma (Grp3/4). 5-year PFS for 52 patients ≥ 4 years was 59.4 (± 7.1) %, receiving either upfront craniospinal irradiation (CSI) or SKK-sandwich chemotherapy (CT). Outcomes did not differ between these strategies (5-year PFS: CSI 61.7 ± 9.9%, SKK-CT 56.7 ± 6.1%). For patients < 4 years (n = 18), 5-year PFS was 50.0 (± 13.2) %. M1-persistence occurred exclusively using postoperative CT and was a strong negative predictive factor (p$_{PFS/OS}$ < 0.01). Patients with additional clinical or molecular high-risk (HR) characteristics had worse outcomes (5-year PFS 42.7 ± 10.6% vs. 64.0 ± 7.0%, p = 0.03). In n = 22 patients ≥ 4 years with full molecular information and without additional HR characteristics, risk classification by molecular subtyping had an effect on 5-year PFS (HR 16.7 ± 15.2%, SR 77.8 ± 13.9%; p = 0.01). CONCLUSIONS: Our results confirm that M1-only is a high-risk condition, and further underline the importance of CSF staging. Specific risk stratification of affected patients needs attention in future discussions for trials and treatment recommendations. Future patients without contraindications may benefit from upfront CSI by sparing risks related to higher cumulative CT applied in sandwich regimen

Clinical and molecular characterization of isolated M1 disease in pediatric medulloblastoma: experience from the German HIT-MED studies

PURPOSE: To evaluate the clinical impact of isolated spread of medulloblastoma cells into cerebrospinal fluid without additional macroscopic metastases (M1-only). METHODS: The HIT-MED database was searched for pediatric patients with M1-only medulloblastoma diagnosed from 2000 to 2019. Corresponding clinical and molecular data was evaluated. Treatment was stratified by age and changed over time for older patients. RESULTS: 70 patients with centrally reviewed M1-only disease were identified. Clinical data was available for all and molecular data for 45/70 cases. 91% were non-WNT/non-SHH medulloblastoma (Grp3/4). 5-year PFS for 52 patients ≥ 4 years was 59.4 (± 7.1) %, receiving either upfront craniospinal irradiation (CSI) or SKK-sandwich chemotherapy (CT). Outcomes did not differ between these strategies (5-year PFS: CSI 61.7 ± 9.9%, SKK-CT 56.7 ± 6.1%). For patients < 4 years (n = 18), 5-year PFS was 50.0 (± 13.2) %. M1-persistence occurred exclusively using postoperative CT and was a strong negative predictive factor (p(PFS/OS) < 0.01). Patients with additional clinical or molecular high-risk (HR) characteristics had worse outcomes (5-year PFS 42.7 ± 10.6% vs. 64.0 ± 7.0%, p = 0.03). In n = 22 patients ≥ 4 years with full molecular information and without additional HR characteristics, risk classification by molecular subtyping had an effect on 5-year PFS (HR 16.7 ± 15.2%, SR 77.8 ± 13.9%; p = 0.01). CONCLUSIONS: Our results confirm that M1-only is a high-risk condition, and further underline the importance of CSF staging. Specific risk stratification of affected patients needs attention in future discussions for trials and treatment recommendations. Future patients without contraindications may benefit from upfront CSI by sparing risks related to higher cumulative CT applied in sandwich regimen. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s11060-021-03913-5

20,000 years of societal vulnerability and adaptation to climate change in southwest Asia.

The Fertile Crescent, its hilly flanks and surrounding drylands has been a critical region for studying how climate has influenced societal change, and this review focuses on the region over the last 20,000 years. The complex social, economic, and environmental landscapes in the region today are not new phenomena and understanding their interactions requires a nuanced, multidisciplinary understanding of the past. This review builds on a history of collaboration between the social and natural palaeoscience disciplines. We provide a multidisciplinary, multiscalar perspective on the relevance of past climate, environmental, and archaeological research in assessing present day vulnerabilities and risks for the populations of southwest Asia. We discuss the complexity of palaeoclimatic data interpretation, particularly in relation to hydrology, and provide an overview of key time periods of palaeoclimatic interest. We discuss the critical role that vegetation plays in the human-climate-environment nexus and discuss the implications of the available palaeoclimate and archaeological data, and their interpretation, for palaeonarratives of the region, both climatically and socially. We also provide an overview of how modelling can improve our understanding of past climate impacts and associated change in risk to societies. We conclude by looking to future work, and identify themes of "scale" and "seasonality" as still requiring further focus. We suggest that by appreciating a given locale's place in the regional hydroscape, be it an archaeological site or palaeoenvironmental archive, more robust links to climate can be made where appropriate and interpretations drawn will demand the resolution of factors acting across multiple scales. This article is categorized under:Human Water > Water as Imagined and RepresentedScience of Water > Water and Environmental ChangeWater and Life > Nature of Freshwater Ecosystems

Therapeutic implications of improved molecular diagnostics for rare CNS-embryonal tumor entities: results of an international, retrospective study

BACKGROUND: Only few data are available on treatment-associated behavior of distinct rare CNS-embryonal tumor entities previously treated as "CNS-primitive neuroectodermal tumors" (CNS-PNET). Respective data on specific entities, including CNS neuroblastoma, FOXR2 activated (CNS NB-FOXR2), and embryonal tumor with multi-layered rosettes (ETMR) are needed for development of differentiated treatment strategies. METHODS: Within this retrospective, international study, tumor samples of clinically well-annotated patients with the original diagnosis of CNS-PNET were analyzed using DNA methylation arrays (n=307). Additional cases (n=66) with DNA methylation pattern of CNS NB-FOXR2 were included irrespective of initial histological diagnosis. Pooled clinical data (n=292) were descriptively analyzed. RESULTS: DNA methylation profiling of "CNS-PNET" classified 58(19%) cases as ETMR, 57(19%) as HGG, 36(12%) as CNS NB-FOXR2, and 89(29%) cases were classified into 18 other entities. Sixty-seven (22%) cases did not show DNA methylation patterns similar to established CNS tumor reference classes. Best treatment results were achieved for CNS NB-FOXR2 patients (5-year PFS: 63%±7%, OS: 85%±5%, n=63), with 35/42 progression-free survivors after upfront craniospinal irradiation (CSI) and chemotherapy. The worst outcome was seen for ETMR and HGG patients with 5-year PFS of 18%±6% and 22%±7%, and 5-year OS of 24%±6% and 25%±7%, respectively. CONCLUSION: The historically reported poor outcome of CNS-PNET patients becomes highly variable when tumors are molecularly classified based on DNA methylation profiling. Patients with CNS NB-FOXR2 responded well to current treatments and a standard-risk-CSI based regimen may be prospectively evaluated. The poor outcome of ETMR across applied treatment strategies substantiates the necessity for evaluation of novel treatments